Gel-Based Lipstick Having Improved Rheology

ABSTRACT

Gel-based lipstick compositions are disclosed comprising an ester terminated poly(ester-amide) (ETPEA) polymeric gellant, a first wax component having a melting point above the sol-gel transition temperature of the ETPEA gellant, a second wax compositions having a melting point equal to of below the sol-gel transition temperature of the ETPEA gellant, optionally a silicone T-resin co-gellant, and one or more oils capable of forming a gel with the ETPEA gellant. The gel compositions are solid or semi-solid at room temperature and are capable of being molded into self-supporting sticks. The disclosed gels provide high gloss films when applied to the lips and/or provide a rheology characterized by a high viscosity over repeated shear cycles.

FIELD OF INVENTION

The present invention relates generally to cosmetic compositions for thelips. More specifically, the invention relates to ester-terminatedpoly(ester-amide) (“ETPEA”) gel-based compositions for imparting highgloss to the lips and/or for imparting films on the lips having enhancedrheological attributes of slip and feel.

BACKGROUND OF THE INVENTION

Conventional lipstick products typically comprise pigments and oilsdispersed in a wax base. The wax base serves to provide the necessarystiffness and physical stability so that the composition can be in theform of a self-supporting stick desired by consumers. However, as aconsequence of the high wax levels typically required to achieve thesecharacteristics, conventional lipsticks suffer several disadvantages.Notably, they do not deliver a high gloss finish, are readilytransferred from the lips to clothing, napkins, cups and the like, andexhibit undesirable bleeding of the pigments and oils from the product(syneresis). Recent approaches to overcoming some of the disadvantagesof waxy lipsticks have centered primarily on the use of polymeric filmformers in addition to, or as a partial replacement for, conventionalwaxy components in order to provide more robust films that are lessprone to transfer and longer wearing. However, such products haveheretofore not been able to achieve a high gloss, primarily because theopaque waxes dull the finish. Further, the wax structure of conventionallipsticks is known to break down under shear encountered during normalwear and rapidly lose the unctuous feeling of freshly applied product.

So-called “lip gloss” products are also known which deliver a glossyfinish and maintain a satisfactory oily rheology during wear but are notdurable and must be frequently reapplied to the lips to maintain thedesired finish. Lip gloss products are typically transparent ortranslucent oil-based formulations which may also comprise low levels ofcolorant. High shine lip glosses are usually high viscosity liquids andtherefore cannot be delivered in the convenient form of a selfsupporting stick but rather are packaged in tubes, pots, and the likeand are typically applied to the lips with the fingers or an applicator.

There is a continuing need in the art for lip products, particularlylipsticks and lip glosses that overcome one or more of the foregoingdeficiencies of conventional lip products. It would be desirable tocombine the convenience and deep color of a lipstick with the high glossand desirable rheology of a lip gloss to provide lip products,particularly pigmented lip products in stick form, which providesuperior gloss, slip, feel, payoff, and/or wear. It is therefore anobject of the invention to provide lip products in stick form whichdeliver a high gloss. It is yet another object of the invention toprovide low-wax content lip products having a hardness sufficient forforming a self-supporting stick. It is a further object of the inventionto provide lip products in stick form which have a rheologycharacterized by an unctuous feel which does not diminish during wear.

SUMMARY OF THE INVENTION

In accordance with the foregoing objectives and others, the presentinvention provides gel-based compositions which impart a high gloss filmon the lips and/or provide an improved rheology. The gel-basedcompositions of the invention are capable of forming self-supportingsolids or semi-solids at room temperature, even in the absence ofsubstantial quantities of wax conventionally required to provide body tolipsticks. This property advantageously allows for the compositions tobe formulated as low wax content lipsticks which further contributes toa high gloss finish, as conventional levels of waxes are known todiminish gloss. Further, the use of a gel-based matrix, rather than awax-based matrix, provides a rheology characterized by a longer-lastingunctuous feel on the lips.

The compositions exhibit a gelled structure comprising a matrix of anester terminated poly(ester-amide) polymer which is capable of gellingnon-polar and low-polarity oils, such as hydrocarbons and fatty esters,alone or in combination with a silicone T-resin co-gellant. Thecompositions typically comprise a first wax component comprising atleast one wax having a melting point above the sol-gel transitiontemperature T_(gel) of the ester terminated poly(ester-amide) polymerand a second wax component having a melting point comparable to or belowthe sol-gel transition temperature T_(gel) of the ester terminatedpoly(ester-amide) polymer. The combination of the gelled matrix withhigh and low melting point waxes contributes a desirable rheologycharacterized by a slip and feel heretofore only obtainable with liquidlip products. Further, the gel network is inherently transparent andthus the gloss of the oily components is not compromised.

In one aspect of the invention, compositions are provided for impartingan unctuous film to the lips comprising: (a) from about 0.1 to about 40%by weight of an ester terminated poly(ester-amide) polymer having anaverage molecular weight between about 3,000 and about 7,500 Daltons andbeing capable of forming a gel with low-polarity and nonpolar oils at orbelow a sol-gel transition temperature T_(gel) wherein T_(gel) is abovebody temperature; (b) from about 0.1 to about 20% by weight of a firstwax component comprising one or more waxes having a melting point aboveT_(gel); (c) from about 0.1 to about 20% by weight of a second waxcomponent comprising one or more waxes having a melting point at orbelow T_(gel); and (e) one or more low-polarity or nonpolar oils capableof forming a gel with the ester terminated poly(ester-amide) polymer ator below the sol-gel transition temperature T_(gel); wherein the one ormore low-polarity or nonpolar oils are selected from the groupconsisting of esters, hydrocarbons, and silicone-based oils; wherein thecomposition is characterized by a viscosity measured during a secondshear cycle that is within ±20% of the viscosity measured during a firstshear cycle at every shear rate between about 1 and about 10 sec⁻¹,wherein the first and the second shear cycles are identical and compriseincreasing shear rates from about 1 to about 1,000 sec⁻¹. Thecompositions provide for enhanced rheological properties including slipand feel on application and during wear as compared to conventionalwax-based lipsticks.

In another aspect, composition for imparting an unctuous film to thelips are provided comprising: (a) from about 0.1 to about 40% by weightBis-Stearyl Ethylenediamine/Neopentyl Glycol/Stearyl Hydrogenated DimerDilinoleate copolymer having an average molecular weight between about5,000 and about 6,000 Daltons and being capable of forming a gel withlow-polarity and nonpolar oils at or below a sol-gel transitiontemperature T_(gel) between about 70 and about 85° C.; (b) from about0.1 to about 20% by weight of a first wax component comprising one ormore waxes having a melting point above T_(gel); (c) from about 0.1 toabout 20% by weight of a second wax component comprising one or morewaxes having a melting point at or below T_(gel); and (e) one or morelow-polarity or nonpolar oils capable of forming a gel with the ETPEApolymer at or below the sol-gel transition temperature T_(gel); whereinsaid one or more low-polarity or nonpolar oils are selected from thegroup consisting of esters, hydrocarbons, and silicone-based oils;wherein the composition is characterized by a viscosity measured duringa second shear cycle that is within ±20% of the viscosity measuredduring a first shear cycle at every shear rate between about 1 and about10 sec⁻¹, wherein the first and said second shear cycles are identicaland comprise increasing shear rates from about 1 to about 1,000 sec⁻¹;and wherein the composition is characterized by: (i) a viscosity greaterthan about 100 Pa·sec at shear rates between about 1 and about 5 sec⁻¹when measured during the first and second shear cycles; and (ii) aviscosity greater than about 10 Pa·sec at shear rates between about 10and about 50 sec⁻¹ when measured during the first and second shearcycles; and (iii) a viscosity greater than about 1 Pa·sec at a shearrate of about 100 sec⁻¹ when measured during the first and second shearcycles.

Methods for imparting an unctuous film to the lips are also providedgenerally comprising applying to the lips any of the gel-based lipstickcompositions described herein.

In a further aspect of the invention cosmetic compositions for impartinga film having improved rheology and/or imparting gloss to the lips areprovided comprising: (a) from about 0.1 to about 40% by weight of anester terminated poly(ester-amide) polymer (“ETPEA”) having an averagemolecular weight between about 3,000 and about 7,500 Daltons and beingcapable of forming a gel with low-polarity and nonpolar oils at or belowa sol-gel transition temperature T_(gel), wherein T_(gel) is above bodytemperature; (b) from about 0.1 to about 20% by weight of a first waxcomponent comprising one or more waxes having a melting point aboveT_(gel); (c) from about 0.1 to about 20% by weight of a second waxcomponent comprising one or more waxes having a melting point comparableto, equal to, or below T_(gel); (d) from about 0.1 to about 25% byweight of a silicone T-resin having a refractive index of at least 1.43when measured as a film at 25° C.; and (e) one or more low-polarity ornonpolar oils which are capable of forming a gel with the ETPEA polymerat or below the sol-gel transition temperature T_(gel) of the ETPEApolymer. Typically, the one or more low-polarity or nonpolar oils areselected from the group consisting of fatty esters, hydrocarbons, andsilicone-based oils, and combinations thereof.

In another aspect of the invention, cosmetic compositions for impartinga film having improved rheology and/or imparting gloss to the lips areprovided as self-supporting compositions, without the need for highlevels of wax, i.e., greater than about 12% by weight, required inconventional formulations. The cosmetic compositions according to thisaspect of the invention comprise: (a) from about 0.1 to about 40% byweight of the ETPEA polymer having the INCI name Bis-StearylEthylenediamine/Neopentyl Glycol/Stearyl Hydrogenated Dimer Dilinoleatecopolymer and having an average molecular weight between about 3,000 andabout 7,500 Daltons and being capable of forming a gel with low-polarityand nonpolar oils at or below a sol-gel transition temperature T_(gel)of the ETPEA polymer, wherein T_(gel) of the ETPEA polymer is betweenabout 70° C. and about 85° C.; (b) from about 0.1 to about 12% by weightof a first wax component comprising one or more waxes having a meltingpoint above about T_(gel) of the ETPEA polymer and below about 110° C.;(c) from about 0.1 to about 12% by weight of a second wax componentcomprising one or more waxes having a melting point comparable to, equalto, or below T_(gel) of the ETPEA polymer and above about 45° C.; (d)from about 0.1 to about 25% by weight of an alkyl phenyl silsesquioxaneT-resin having a refractive index of at least 1.43 when measured as afilm at 25° C.; wherein the at least one alkyl phenyl silsesquioxaneresin comprises siloxy moieties:

[RSiO_(3/2)]_(a)[R¹SiO_(3/2)]_(b)[R²SiO_(3/2)]_(c)[R³ ₃SiO_(1/2)]_(d)[R³₂SiO_(2/2)]_(e)[SiO_(4/2)]_(f)

where R is methyl; R¹ is C₂₋₂₀ alkyl or C₅₋₂₀ cycloalkyl; R² is phenyl,R³ is C₁₋₂₀ alkyl, C₅₋₂₀ cycloalkyl, C₇₋₁₄ aralkyl, C₇₋₁₄ alkaryl, orC₆₋₁₀ aryl; and a, b, and c are such that their respective siloxy groupstogether comprise at least 90 mol percent of the total of siloxymoieties, and d, e, and f are such that their respective moietiestogether comprise less than 10 mol percent of all of siloxy moieties;and (e) one or more low-polarity or nonpolar oils capable of forming agel with the ETPEA polymer at or below the sol-gel transitiontemperature T_(gel) of the ETPEA polymer, wherein the one or morelow-polarity or nonpolar oils are selected from the group consisting offatty esters, hydrocarbons, and silicone-based oils. Preferably, thefirst and second wax components collectively comprise about 12% or lessby weight of said composition, i.e., below conventional wax levels for alipstick. The composition is nevertheless self-supporting at roomtemperature such that it is capable of being formulated as a lipstickand the like. The composition has a hardness at room temperature of atleast 40 g.

In yet another aspect of the invention, cosmetic compositions forimparting a film having improved rheology and/or imparting gloss to thelips are provided comprising: (a) from about 0.1 to about 40% by weightof the ETPEA polymer having the INCI name Bis-StearylEthylenediamine/Neopentyl Glycol/Stearyl Hydrogenated Dimer Dilinoleatecopolymer and having an average molecular weight between about 5,000 andabout 6,000 Daltons and being capable of forming a gel with low-polarityand nonpolar oils at or below a sol-gel transition temperature T_(gel)of the ETPEA polymer between 70 and about 85° C.; (b) from about 0.1 toabout 20% by weight of a first wax component comprising one or morewaxes selected from the group consisting of linear polyethylene wax,microcrystalline petroleum wax, and combinations thereof; (c) from about0.1 to about 20% by weight of a second wax component comprisingozokerite wax; (d) from about 0.1 to about 25% by weight of a phenylsilsesquioxane T-resin having a refractive index of at least 1.50measured as a film at 25° C.; (e) one or more low-polarity or nonpolaroils capable of forming a gel with the Bis-StearylEthylenediamine/Neopentyl Glycol/Stearyl Hydrogenated Dimer Dilinoleatecopolymer at or below the sol-gel transition temperature T_(gel);wherein the one or more low-polarity or nonpolar oils are selected fromthe group consisting of fatty esters, hydrocarbons, and silicone-basedoils; and (f) from 0.1 to about 10% by weight of one or more pearlingagents; wherein said composition exhibits a gloss across the entirerange of 0.1 to about 10% by weight one or more pearling agents withinabout 10% of the gloss of an otherwise identical composition in theabsence of said one or more pearling agents, as measured at an angle of85°. The composition typically has a hardness at room temperature of atleast 40 g, but preferably will have a substantially greater hardness,typically between about 200 and about 300 g. Surprisingly, even suchrelatively hard sticks have excellent “pay off” such that uponapplication to the lips an acceptable amount of product is transferredto the lips.

Methods for imparting high gloss to the lips are also providedcomprising applying the inventive compositions to the lips. Thecompositions typically have a gloss of at least about 65, more typicallyat least about 70, preferably at least about 75, and more preferably atleast about 80, when measured at 85 degrees. In some embodiment of theinvention, the compositions will have a gloss of about 85 or greater,about 90 or greater, or about 95 or greater when measured at 85 degrees.

While the preferred lipsticks according to the invention have bothimproved rheology and impart high gloss, it will be understood that, inthe broadest aspect, the invention is not limited to any particulargloss level, as the improved rheology will find significant applicationregardless of gloss. Further, while the preferred embodiments of theinvention involve compositions having a hardness suitable forformulating the compositions in stick form, the invention is not solimited and embraces compositions of any hardness, including liquids,viscous liquids, semi-solids, and solids, as the improved rheologicalattributes described herein are contemplated to benefit liquid lip glossproducts as well as lipsticks.

These and other aspects of the invention will be better understood byreference to the following Detailed Description, including the Figuresand appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 compares the 85 degree gloss of a lipstick according to theinvention (A) with the gloss of liquid lip gloss product (B), severalcommercially available wax-based lipsticks (C—N), and a two-part lipproduct having a transparent top coat (O).

FIG. 2 shows the solubility space for an ETPEA polymeric gellant whereineach marker “⋄” represents the Hansen Solubility Parameter pair(δ_(p),δ_(H)) for various solvents and the letters representformulations of a particular solvent with the ETPEA polymer at a polymercontent of 15% by weight, where “G” is indicates a firm, clear gel;“G_(h)” indicates a firm, hazy gel; “M” indicates a cloudy, white solid;“S” indicates that the polymer was soluble in that solvent; “S_(p)”indicates that a cloudy partial solution was formed; and “I” indicatesthat the polymer was incompatible with the solvent.

FIG. 3 compares the specular reflection at 85 degrees for and ETPEAgel-based lipstick (Δ) and a conventional wax-based lipstick (□) at thevarious pearl and mica loadings.

FIG. 4 shows the viscosity of a conventional wax-based lipstick as afunction of shear rate over a first shear cycle (⋄) and a second shearcycle (□).

FIG. 5 shows the viscosity of an ETPEA gel-based lipstick as a functionof shear rate over a first shear cycle (⋄) and a second shear cycle (□).

DETAILED DESCRIPTION

As used herein, all terms are intended to have their ordinary andaccustomed meaning in the art unless otherwise explicitly defined.

The present invention is founded on the discovery that the use of esterterminated poly(ester-amide) (“ETPEA”) polymers in combination withcertain co-gellants and waxes in cosmetic compositions, such aslipsticks and the like, provide products having high gloss and superiorrheology. In addition to the ETPEA polymer, the compositions typicallycomprise a co-gellant, ideally a high molecular weight silicone T-resin,a first wax component and a second wax component. The first waxcomponent comprises at least one wax having a melting point above thesol-gel transition temperature T_(gel) of the ETPEA polymer and thesecond wax component comprises at least one wax having a melting pointcomparable to, equal to, or below the sol-gel transition temperatureT_(gel) of the ETPEA polymer.

As used herein, the term “comparable to,” when used in reference to themelting point of the second wax component, means that the melting pointrange of the wax may, at the upper end or the melting range, be somewhatgreater than T_(gel) of the ETPEA polymer, but in no event greater thanabout 6° C., preferably no greater than about 3° C., and morepreferably, no greater than about 1° C. The importance being that as thecomposition is cooled from an initial liquid state at high temperature,the second wax component begins to crystallize or otherwise solidifysimultaneously with, or after, the onset of gellation of the ETPEApolymer such that the second wax component is constrained within the gelnetwork of the ETPEA polymer, preferably, but not necessarily, as amicrodispersion. Because the first wax component crystallizes orotherwise solidifies above T_(gel) of the ETPEA polymer, no suchconstraint on its solidification is imposed by the composition.

The ETPEA polymer and both wax components are selected such that T_(gel)of the ETPEA polymer and the melting point of both the first and secondwax components are above room temperature (about 23° C.) and,preferably, above body temperature (about 36-38° C.), such that theETPEA polymer remains gelled and the waxes remain solid during wear,i.e., when applied as a film to the lips, and during storage underambient conditions.

In one embodiment, the cosmetic compositions for imparting a film havingimproved rheology and/or imparting gloss to the lips will comprise:

-   -   (a) from about 0.1 to about 40% by weight of an ester terminated        poly(ester-amide) polymer having an average molecular weight        between about 3,000 and about 7,500 Daltons and being capable of        forming a gel with low-polarity and nonpolar oils at or below a        sol-gel transition temperature T_(gel) wherein T_(gel) is above        body temperature;    -   (b) from about 0.1 to about 20% by weight of a first wax        component comprising one or more waxes having a melting point        above T_(gel);    -   (c) from about 0.1 to about 20% by weight of a second wax        component comprising one or more waxes having a melting point at        or below T_(gel);    -   (d) from about 0.1 to about 25% by weight of a silicone T-resin        and a refractive index of at least 1.43 measured as a film at        25° C.;    -   (e) one or more low-polarity or nonpolar oils soluble capable of        forming a gel with said ester terminated poly(ester-amide)        polymer at or below said sol-gel transition temperature T_(gel);        wherein said one or more low-polarity or nonpolar oils are        selected from the group consisting of esters, hydrocarbons, and        silicone-based oils;        wherein the composition has a gloss of at least about 70        (preferably at least 75, 80, or 85) when measured at 85 degrees.        As shown in FIG. 1, the lipstick compositions of the invention,        indicated by “A,” provide higher gloss than commercially        available wax-based lipsticks (labeled C—N and identified        elsewhere herein), as well as a representative liquid lip gloss        (“B”) and a two-part lipstick comprising a clear top coat (“O”).

The various components of the composition are described below.

ETPEA Polymer

The ETPEA polymer is a necessary component of the inventivecompositions. In the broadest aspects, any ETPEA polymer compatible withcosmetic use is contemplated to be suitable, provided the polymer iscapable of existing as a gel at room temperature and, preferably, atbody temperature. In that regard, the sol-gel transition temperatureT_(gel) of the ETPEA polymer is typically above about 40° C., moretypically, above about 50° C., preferably above about 60° C., and morepreferably above about 70° C. In a currently preferred embodiment, theETPEA polymer has a T_(gel) between about 70° C. and about 85° C.,including a representative embodiments having a T_(gel) of about 70° C.,about 75° C., about 80° C., and about 85° C. While not strictlyidentical, the softening point, as measured by, for example,differential scanning calorimetry (DSC), of the ETPEA polymer willprovide useful for approximating the sol-gel transition temperatureT_(gel) as this is the point where the hydrogen bonding network of thepolymer gel begins to break down. In some embodiments, the ETPEA polymerwill have a softening point of between about 70° C. and about 85° C.,including about 70° C., about 75° C., about 80° C., and about 85° C.

Non-limiting examples of suitable ETPA polymers and methods of makingthe same are described in U.S. Pat. Nos. 6,552,160 and 6,875,245, thedisclosures of which are hereby incorporated by reference in theirentirety.

Generally, the ETPA polymer may be a random, alternating, or blockcopolymer comprising units A and B attached to one another through esterand/or amide linkages and terminated by ester linkages to a terminatinggroups, wherein:

(a) unit A has the structure:

wherein,

-   R is a linear, branched, or cyclic alkyl group having from 4 to 70    carbon atoms, optionally comprising: (i) one or more unsaturated    bonds; (ii) one or more aliphatic or aromatic rings; and/or (iii)    one or more heteroatoms selected from the group consisting of    halogen, oxygen, nitrogen, and sulfur; and wherein R optionally    comprises one or more groups —(C═O)—O— linking R to additional units    of A or B; wherein R is independently selected at each occurrence of    unit A; and-   R₁ is a radical having from 2 to 36 carbon atoms selected from the    group consisting of linear, branched, or cyclic alkyl groups, aryl    groups, or heteroaryl groups, and combinations thereof, optionally    comprising: (i) one or more unsaturated bonds; (ii) one or more    aliphatic or aromatic rings; and/or (iii) one or more heteroatoms    selected from the group consisting of halogen, oxygen, nitrogen, and    sulfur; wherein R₁ is independently selected at each occurrence of    unit A;-   R* is independently selected, at each occurrence, from hydrogen,    aryl, and linear, branched, or cyclic alkyl group having from 1 to    10 carbon atoms, optionally comprising: (i) one or more unsaturated    bonds; (ii) one or more aliphatic or aromatic rings; and/or (iii)    one or more heteroatoms selected from the group consisting of    halogen, oxygen, nitrogen, and sulfur; and wherein independently    each R* may, together with R₁ or with the other R*, form a    heterocyclic ring;    (b) unit B has the structure:

wherein R is as defined above and is independently selected at eachoccurrence of B, and R₂ is a linear, branched, or cyclic alkyl grouphaving from 2 to 20 carbon atoms, optionally comprising: (i) one or moreunsaturated bonds; (ii) one or more aliphatic or aromatic rings; and/or(iii) one or more heteroatoms selected from the group consisting ofhalogen, oxygen, nitrogen, and sulfur; and wherein R₂ may optionallycomprise between 1 and 4 groups of the form —O— linking R₂ to additionalunits of A or B; wherein R₂ is independently selected at each occurrenceof unit B; and(c) terminal groups of the form R₃O— form an ester linkage with theterminal carbonyl group of unit A and/or unit B, wherein R₃ isindependently, at each terminal group, a linear, branched, or cyclicalkyl group having from 10 to 30 carbon atoms, optionally comprising:(i) one or more unsaturated bonds; (ii) one or more aliphatic oraromatic rings; and/or (iii) one or more heteroatoms selected from thegroup consisting of halogen, oxygen, nitrogen, and sulfur.

In some embodiments, R is the same at each occurrence of units A and/orB in the polymer. In other embodiments, R may be different at one ormore occurrences of units A and/or B. Likewise or R₁ and/or R₂ arepreferably the same at each occurrence of units A and/or B in thepolymer, but may also be different at each occurrence. By the phrase “ateach occurrence of unit A” is meant that, of the plurality of units of Acontained in the polymer, any given unit A may be different from one ormore other units of A by virtue of the selection of R and R₁. Likewise,the phrase “at each occurrence of unit B” means that of the plurality ofunits of B contained in the polymer, each individual unit B may bedifferent from one or more other units of B by virtue of the selectionof R and R₂. That is, for example, if R₁ is a group —CH₂—CH₂—, eachinstance of unit A may contain the same group —CH₂—CH₂— for R₁ or maycontain different groups for R₁. For example, R₁ may be a group—CH₂—CH₂— at some instances of unit A and a group, for example,—CH₂—(CH₂)₁₋₄—CH₂—, at other occurrences of unit A. In one embodiment,one or more of R, R₁, and R₂ is the same at every occurrence of units Aand/or B in the polymer.

In the preferred ETPEA polymers according to the invention, at one ormore occurrence of unit A, each R* is hydrogen and R₁ is a group—(CR′R″)_(n)— wherein n is an integer from 2 to 12, and R′ and R″ areindependently at each occurrence selected from the group consisting ofhydrogen, methyl, ethyl, propyl, and butyl. In a preferred embodiment,R₁ is —(CH₂)₂— at every occurrence of unit A. In other embodiments, R₁is —(CH₂)₂— in at least 80%, preferably at least 90% and more preferablyat least 95% of the occurrences of unit A.

Preferably R₂, at one or more occurrence of unit B, is selected from thegroup consisting of —(CH₂)_(n)—, —CH₂—CR′H—, and —CH₂—CR′R″—CH₂—,wherein n is an integer from 2 to 6, R′ and R″ are independentlyhydrogen or an alkyl or aryl group having from 1 to 12 carbon atoms andoptionally comprising between 1 and 4 groups of the form —O— linking R′and/or R″ to additional units of A or B and/or optionally including oneor more groups of the form —OH. In a preferred embodiment R₂, at one ormore occurrence of unit B, is a divalent neopentyl group (neopentylene),including groups of the form —CH₂—C(CH₃)₂—CH₂—.

In a preferred embodiment, R₁ is —(CH₂)₂— in at least 95% and preferablyin each of the occurrences of unit A and R₂ is —CH₂—C(CH₃)₂—CH₂— in atleast 95% and preferably in each of the occurrences of unit B.

Preferably, at one or more occurrence of unit A and/or unit B, R isindependently at each occurrence, a group having the structure:

wherein a, b, c, and d are independently integers from 1 to 20. Oneskilled in the art will appreciate that groups of this form correspondto the alkyl portion of hydrogenated fatty acid dimers, such as thereaction product formed by heating C₁₈ unsaturated fatty acids (oleic,linoleic, linolenic acids and the like) in the presence of a claycatalyst followed by hydrogenation. Stated in another way, R may beselected, independently at each occurrence, from divalent alkyl groupscorresponding to the alkyl portion (i.e., excluding the —C(═O)—OHfunctional groups) of dimer acids formed by the dimerization reaction ofunsaturated fatty acids having from 5 to 30 carbon atoms, preferably C₁₈unsaturated fatty acids such as oleic, linoleic, linolenic, and tall oilfatty acids.

In one embodiment, the ETPEA polymer is a random copolymer comprising nequivalents of unit A and m equivalents of unit B, wherein n and m areselected to provide a polymer having an average molecular weight betweenabout 3,000 and about 7,500 Daltons. Preferably, n and m are selected toprovide a polymer having an average molecular weight between about 5,000and about 6,000, and more preferably about 5,500 Daltons.

Suitable ETPEA polymers may be prepared from dibasic acid, diamine,polyol and monoalcohol components, as described, for example, in U.S.Pat. No. 6,552,160, the disclosure of which is hereby incorporated byreference. Briefly, ETPEA polymers may be prepared by reacting wequivalents of hydroxyl from polyol or a reactive equivalent thereof, xequivalents of carboxylic acid from diacid or a reactive equivalentthereof, y equivalents of amine from diamine, and z equivalents ofhydroxyl from monoalcohol or a reactive equivalent thereof; whereinw/(w+y+z) is within the range of about 0.05 to 0.45; y/(w+y+z) is withinthe range of about 0.25 to 0.75; and z/(w+y+z) is within the range of0.20 to 0.50; under reactions conditions to provide a resin compositionhaving an acid number of less than 20 and an amine number of less than20, wherein at least about 50% of the carboxylic acid equivalents arefrom polymerized fatty acid, at least about 50% of the amine equivalentsare from ethylene diamine, and mono-alcohol is substantially the onlymonofunctional reactant used to form the resin. Preferably, 10-60equivalent percent of the total of the hydroxyl and amine equivalentsprovided by diamine, polyol and monoalcohol are provided by monoalcohol;and no more than 50 equivalent percent of the total of the hydroxyl andamine equivalents provided by diamine, polyol and monoalcohol areprovided by polyol. Preferably, polymerized fatty acid constitutes atleast 75 equivalent percent, and more preferably, at least about 90equivalent percent of the acid equivalents of the dibasic acid.Elthylene diamine preferably constitutes at least about 70 equivalentpercent of the amine equivalents from diamine.

The selection of dibasic acid, diamine, polyol and monoalcohol ispreferably as described in U.S. Pat. No. 6,552,160, the disclosure ofwhich is hereby incorporated by reference. Briefly, preferred dibasicacids are polymerized fatty acids formed from oleic acid, linoleic acid,linolenic acid, tall oil fatty acid and the like. The polymerized fattyacid is preferably hydrogenated before use. Preferably, the diaminereactant is ethylene diamine. Preferred monoalcohol (i.e., monohydricalcohol) reactants include formula R₃OH, wherein R₃ is preferably ahydrocarbon group having at least ten carbon atoms, such as, forexample, 1-dodecanol, 1-tetradecanol, 1-hexadecanol (cetyl alcohol),1-octadecanol (stearyl alcohol), 1-eicosanol (arachidyl alcohol) and1-docosanol (behenyl alcohol), and the like. Preferred polyols includewithout limitation ethylene glycol, propylene glycol, butylene glycol,glycerol, trimethylolpropane, pentaerythritol, neopentyl glycol,tris(hydroxylmethyl)methanol, di-pentaerythritol, andtri-pentaerthyritol, and the like. In addition to polymerized fattyacids and ethylene diamine, other diacids and diamines may also bepresent. Suitable “co-diacids” and “co-diamines” include, but are notlimited to, those described in U.S. Pat. No. 6,552,160, incorporatedherein by reference.

The currently preferred ETPEA polymer according to the present inventionis, according to the nomenclature of INCI, a Bis-StearylEthylenediamine/Neopentyl Glycol/Stearyl Hydrogenated Dimer Dilinoleatecopolymer, commercially available from Arizona Chemical (Jacksonville,Fla.) under the tradename SYLVACLEAR® C75V. This polymer ischaracterized by: a softening point between 75-85° C. as measured by theRing & Ball method of ASTM E28-99, incorporated by reference herein; anacid number of 26 (maximum) as measured by ASTM D803, D65 and D1980,incorporated by reference herein; an amine number of 1 (maximum) asmeasured by ASTM D2073 and D2074, incorporated by reference herein; andan average molecular weight of about 5,500 Daltons.

The ETPEA polymer may suitable comprise from about 0.1 to about 40% byweight of the composition, but typically will comprise between about 0.1to about 25% by weight of the composition. In some embodiments, theETPEA polymer will comprise from about 0.5 to about 15% by weight of thecomposition or from about 0.5 to about 12%. In some embodiments, theETPEA polymer will comprise less of the composition than the lipstickformulations disclosed in U.S. Patent Pub. No. 2005/0197479 to Pavlin,the disclosure of which is hereby incorporated by reference. Thelipstick formulations described in U.S. Patent Pub. No. 2005/0197479 toPavlin typically comprise ETPEA polymer from 15-25% by weight, includingseveral examples of ETPA polymer levels of 18% by weight. Accordingly,in some embodiments the inventive compositions will comprise from 0.1%to less than about 12, 10, 8, 6, or about 5% by weight ETPEA polymer. Inother embodiments, the inventive compositions will contain as little as0.1 to about 2.5% by weight ETPEA polymer, 0.1 to about 2% by weightETPEA polymer, 0.1 to about 1.5% by weight ETPEA polymer, or 0.1 toabout 1% by weight ETPEA polymer. In one interesting variant, the ETPEApolymer will comprise from 0.5 to 1% by weight, or 0.5 to less than 1%by weight of the composition. Suitable lipsticks can been prepared fromcompositions comprise from 0.1-1%, 1-2%, 2-3%, 3-4%, 4-5%, 5-6%, 6-7%,7-8%, 8-9%, 9-10%, 10-11% or 11-12% by weight ETPEA polymer, each rangebeing considered a separate embodiment of the invention. In onerepresentative embodiment, the compositions will comprise between about5 and about 6% by weight ETPEA polymer. The compositions of the presentinvention are believed to provide superior gloss and/or hardness and/orrheology to the lipstick formulations of U.S. Patent Pub. No.2005/0197479.

Waxes

The first wax component may comprise any wax, particularly thosetypically used in lipsticks and other cosmetic products, provided themelting point of the wax is greater than the T_(gel) of the ETPEApolymer. Similarly, the second wax component may comprise anycosmetically acceptable wax provided that the melting point of the waxis comparable to, equal to, or below the T_(gel) of the ETPEA polymer.

The waxes may be natural, mineral and/or synthetic waxes. Natural waxesare those of animal origin, including without limitation beeswax,spermaceti, lanolin, and shellac wax, and those of vegetable origin,including without limitation carnauba, candelilla, bayberry, andsugarcane wax.

Mineral waxes contemplated to be useful include, without limitationozokerite, ceresin, montan, paraffin, microcrystalline, petroleum, andpetrolatum waxes.

Synthetic waxes include, for example, polyethylene glycols such asPEG-18, PEG-20, PEG-32, PEG-75, PEG-90, PEG-100, and PEG-180 which aresold under the tradename Carbowax® (The Dow Chemical Company). Mentionmay be made of Carbowax 1000 which has a molecular weight range of 950to 1,050 and a melting point of about 38° C., Carbowax 1450 which has amolecular weight range of about 1,305 to 1,595 and a melting point ofabout 56° C., Carbowax 3350 which has a molecular weight range of 3,015to 3,685 and a melting point of about 56° C., and Carbowax 8000 whichhas a molecular weight range of 7,000 to 9,000 and a melting point ofabout 61° C.

Synthetic waxes also include Fischer Tropsch (FT) waxes and polyolefinwaxes, such as ethylene homopolymers, ethylene-propylene copolymers, andethylene-hexene copolymers. Representative ethylene homopolymer waxesare commercially available under the tradename POLYWAX® Polyethylene(Baker Hughes Incorporated) with melting points ranging from 80° C. to132° C. Commercially available ethylene-α-olefin copolymer waxes includethose sold under the tradename PETROLITE® Copolymers (Baker HughesIncorporated) with melting points ranging from 95° C. to 115° C.

Table 1 provides several suitable waxes arranged by melting point ormelting range.

TABLE 1 Wax Melting Point (° C.) acrawax 140  microcrystalline petroleumwax 99 linear polyethylene wax 95 stearone 89 castor wax 86 montan wax82-95 lignite wax 82-95 ouricouri wax 81-84 carnauba wax 78-85 rice branwax 77-86 shellac wax 74-78 esparto wax 73 ozokerite wax 72 jojoba wax70 candelilla wax 68-73 ceresin wax 67-71 beeswax 62-64 castor wax 60sugarcane wax 60 stearyl alcohol 59 hard tallow 57-60 cetyl alcohol 56petrolatum 54 glyceryl monostearate 54-56 Japan wax 53 silicone waxes53-75 paraffin wax 50-60 lanolin alcohol 45-60 bayberry wax 45 cetylpalmitate 43-53 lanolin 38-42 illipe butter 34-38 cocoa butter 31-35

It will be understood that the melting points and ranges provided inTable 1 are merely representative of typical values for each wax andwide variation in the melting point or melting point range may beobserved from sample to sample depending on the source and purity of thewax. Thus, for example, ozokerite wax is considered to be useful in thepractice of the invention regardless of whether its melting point isdetermined to be 72° C. or otherwise. It is within the skill in the artto determine the melting point or melting point range of any given waxsample. Melting points may be determined, for example, by drop meltingpoint according to ASTM D127, incorporated by reference herein, and/orring-and-ball softening point according to ASTM D36, incorporated byreference herein.

In a preferred embodiment where the ETPEA polymer has a sol-geltransition temperature T_(gel) of about 70° C. to about 85° C., thefirst wax component comprises one or more waxes having a melting pointabove about 70° C. to about 85° C. which may be selected from the groupconsisting of linear polyethylene, microcrystalline petroleum wax,carnauba wax, lignite wax, ouricouri wax, rice bran wax, castor wax,montan wax, stearone (18-pentatriacontanone), acrawax(N,N′-ethylenebisstearamide), and combinations thereof. Preferably, thefirst wax component comprises linear polyethylene and/ormicrocrystalline petroleum wax.

In the embodiment where the ETPEA polymer has a sol-gel transitiontemperature T_(gel) of about 70° C. to about 85° C., the second waxcomponent has a melting point comparable to, equal to, or below about70° C. to about 85° C. and comprises one or more waxes selected from thegroup consisting of bayberry wax, castor wax, Japan wax, ozokerite wax,beeswax, candelilla wax, petrolatum, ceresin wax, cocoa butter, illipebutter, esparto wax, ethylene glycol diesters or triesters of C₁₈-C₃₆fatty acids, cetyl palmitate, paraffin wax, hard tallow, lanolin,lanolin alcohol, cetyl alcohol, glyceryl monostearate, sugarcane wax,jojoba wax, stearyl alcohol, silicone waxes, and combinations thereof.Preferably, the second wax component comprises ozokerite wax.

In one embodiment, the compositions do not comprise carnauba wax. Inanother embodiment, the compositions do not comprise candelilla wax.

In a preferred embodiment according to the invention, the compositionwill comprise ozokerite wax and at least one, or at least two, otherwaxes. Preferably, at least one of the additional waxes will have amelting point greater than that of the ozokerite wax, and preferably atleast two additional waxes will have a melting point above ozokerite. Inanother embodiment, the composition will comprise ozokerite wax and atleast one, or at least two, other waxes, with the proviso that at leastone of the additional waxes, preferably at least two of the additionalwaxes, are synthetic waxes. In yet another embodiment of the invention,the compositions will comprise ozokerite wax and at least, preferably atleast two, additional waxes selected from microcrystalline petroleum waxand polyolefin wax, including without limitation linear polyethylenewax.

An exemplary composition according to the invention comprises the ETPEAgellant Bis-Stearyl Ethylenediamine/Neopentyl Glycol/StearylHydrogenated Dimer Dilinoleate copolymer and the first wax componentcomprises or consists essentially of microcrystalline petroleum waxand/or linear polyethylene wax and the second wax component comprises orconsists essentially of ozokerite wax. In this context, the phrase“consists essentially of” is intended to exclude any additional waxcomponents, the presence of which would adversely impact one or more ofgloss, hardness, and/or rheology as compared to the same compositionwithout the additional wax(es).

The first and second wax components each are present in the formulationfrom about 0.15 to about 20% by weight based on the total weight of theformulation. Preferably, each wax component comprises from about 0.5 toabout 15% by weight of the total composition. In one embodiment, thefirst and second wax components collectively comprise from about 1 toabout 12% by weight or from about 1 to less than 12% by weight, both ofwhich represent wax levels below the levels conventionally used inlipsticks. In other embodiments, the first wax component comprises fromabout 1, 5, or about 10% to about 12 or about 15% by weight and thesecond wax component comprises from about 0.1, 0.5, 1, or about 5% toabout 5, 10, or about 12% by weight of the total composition. It will beunderstood the first wax component includes all waxes in the compositionhaving melting points above the sol-gel transition temperature T_(gel)of the ETPEA polymer and, likewise, the second wax component comprisesall waxes in the composition having a melting point comparable to, equalto, or below T_(gel) of the ETPEA polymer.

In one embodiment according to the invention, the composition willcomprise from about 0.1 to about 5%, typically from 0.5 to about 3%,more typically from about 0.5 to about 2.5%, and preferably from about 1to about 2% ozokerite wax and at least one, or at least two, other waxeswhose combined weight typically ranges from about 2.5 to about 15%, moretypically from about 3% to about 12%, preferably from about 4% to about10%, and more preferred still from about 5% to about 8% by weight. Inone embodiment, ozokerite wax will comprise from about 1 to about 2% byweight of the composition and at least one, preferably at least two,additional waxes selected from microcrystalline petroleum wax andpolyolefin wax, including without limitation linear polyethylene wax,will comprise from about 5% to about 8% by weight of the totalcomposition.

Typically, the wax component having a melting point comparable to, equalto, or below the sol-gel transition temperature T_(gel) of ETPEA polymer(i.e., the low melting point wax component) will be present in a weightratio to the ETPEA polymer from about 20:1 to about 1:20, more typicallyfrom about 10:1 to about 1:10, and usually from about 5:1, 4:1, 3:1 or2:1 to about 1:2, 1:3, 1:4 or 1:5. In some embodiments, the low meltingpoint wax component will equal or exceed, on a weight basis, the amountof ETPEA polymer such the weight ratio of the low melting point wax,preferably ozokerite, to ETPEA polymer will be greater than 1:1,preferably greater than 1.2:1, or greater than 1.4:1, or greater than1.6:1, or greater than greater than 1.8:1, or greater than 2:1.

Typically, wax component having a melting point above T_(gel) of ETPEApolymer (i.e., the high melting point wax component) will be present ina weight ratio to the ETPEA polymer from about 50:1 to about 1:20, moretypically from about 25:1 to about 1:10, and usually from about 15:1,12:1, 10:1 or 8:1 to about 1:1. In some embodiments, the high meltingpoint wax component will equal or exceed, on a weight basis, the amountof ETPEA polymer such the weight ratio of the high melting point waxcomponent to ETPEA polymer will be greater than 1:1, preferably greaterthan 2:1, or greater than 4:1, or greater than 6:1, or greater thangreater than 8:1, or greater than 10:1.

In some embodiments, the amount of high melting point wax component willexceed the amount low melting point wax component in the compositionsuch that the weight ratio of the high melting point wax component tothe low melting point wax component is from about 1:1 or greater toabout 20:1, typically about 1.5:1 to about 15:1, more typically fromabout 2:1 to about 3:1, 4:1, 5:1 or 10:1.

Silicone T-resin

While not strictly necessary to the practice of the invention, it hasbeen surprisingly found that the incorporation of a silicone resinhaving tertiary connectivity of siloxy units (i.e., a T-resin) as aco-gellant provides a marked improvement in gloss, slip, and feel ofcosmetic products according to the invention. Therefore, preferredembodiments will comprise a silicone T-resin, typically between about0.1 and about 25% by weight of the entire composition.

Suitable silicone T-resins comprise alkyl and/or aryl siloxy groups, butpreferably include aryl siloxy groups such as phenyl siloxy groups, inorder to increase the refractive index of the resin. An example of sucha resin is methyl phenyl silsesquioxane or polyphenyl silsesquioxane.Other suitable silicone T-resins include, without limitation, the C₂₋₂₀alkyl phenyl silsesquioxane resins described in U.S. Patent Pub. No.2004/0180011, the disclosure of which is hereby incorporated byreference. Generally, the disclosed C₂₋₂₀ alkyl phenyl silsesquioxaneresins comprise the following siloxy moieties:

[RSiO_(3/2)]_(a)[R¹SiO_(3/2)]_(b)[R²SiO_(3/2)]_(c)[R³ ₃SiO_(1/2)]_(d)[R³₂SiO_(2/2)]_(e)[SiO_(4/2)]_(f)

where R is methyl; R¹ is C₂₋₂₀ alkyl or C₅₋₂₀ cycloalkyl; R² is phenyl,R³ is C₁₋₂₀ alkyl, C₅₋₂₀ cycloalkyl, C₇₋₁₄ aralkyl, C₇₋₁₄ alkaryl, orC₆₋₁₀ aryl; and a, b, and c are such that their respective siloxy groupstogether comprise at least 90 mol percent of the total of siloxymoieties, preferably b and c collectively comprise 20 to 100 mol percentof the total of siloxy moieties, and d, e, and f are such that theirrespective moieties together comprise less than 10 mol percent of all ofsiloxy moieties, and preferably, d, e, and f are zero.

In one embodiment, a, d, e, and f are zero, and R¹ is C₃₋₈ alkyl,preferably propyl. The most preferred silicone T-resins are propylphenyl silsesquioxane resins comprise the siloxy moieties[CH₃CH₂CH₂SiO_(3/2)]_(b) and [C₆H₅SiO_(3/2)]_(c) where the molar ratiob:c is between about 10:1 to about 1:10, preferably between about 1:1and about 1:5, and more preferably about 1:3. The propyl phenylsilsesquioxane resins will typically have a softening point betweenabout 40° C. and about 50° C., preferably above 45° C., and a refractiveindex typically greater than about 1.4, preferably greater than about1.5, and more preferably greater than or equal to about 1.57 whenmeasured as a film at 25° C.

A currently preferred resin is the propyl phenyl silsesquioxane resinWacker Belsil® SPR 45 VP, available from Wacker Chemical, (Adrian,Mich.). This polymer has a refractive index of 1.55 when measure as aliquid at 82° C. and a refractive index of 1.57 when measured as a filmat 25° C. The silicone T-resin is typically provided in solvent-freefrom, but should be compatible with (i.e., partially solubilize) fattyester oils, silicone oils, and/or hydrocarbons to limit syneresis ofthese components in the finished formulation.

In some embodiments, the silicone T-resin will comprise from about 0.5%,1%, 2%, 3%, 4%, or 5% to about 6%, 7%, 8%, 9%, 10%, 12%, 15%, or 20% ofthe total composition, more typically from about 4-10% of thecompositions, and in one useful embodiment, from about 5-7% of thecomposition.

Non Polar and Low-Polarity Oils

The cosmetic compositions of the invention will include one or morelow-polarity and/or non-polar oils capable of forming a gel with theETPEA polymer. In a preferred embodiment, suitable oils are selectedfrom the group consisting of esters, particularly fatty acid esters;silicone oils; and hydrocarbons.

Ester oils include any non-polar or low-polarity ester, including fattyacid esters. Special mention may be made of those esters commonly usedas emollients in cosmetic formulations. Such esters will typically bethe etherification product of an acid of the form R₄(COOH)₁₋₂ with analcohol of the form R₅(OH)₁₋₃ where R₄ and R₅ are each independentlylinear, branched, or cyclic hydrocarbon groups, optionally containingunsaturated bonds, and having from 1 to 30 carbon atoms, preferably from2 to 30 carbon atoms, and more preferably, from 3 to 30 carbon atoms,optionally substituted with one or more functionalities includinghydroxyl, oxa, oxo, and the like. Preferably, at least one of R₄ and R₅comprises at least 10, and more preferably, at least 15, 16, 17, or 18carbon atoms, such that the ester comprises at least one fatty chain.The esters defined above will include, without limitation, the esters ofmono-acids with mono-alcohols, mono-acids with diols and triols,di-acids with mono-alcohols, and tri-acids with mono-alcohols.

Suitable fatty acid esters include, without limitation, butyl acetate,butyl isostearate, butyl oleate, butyl octyl oleate, cetyl palmitate,ceyl octanoate, cetyl laurate, cetyl lactate, cetyl isononanoate, cetylstearate, diisostearyl fumarate, diisostearyl malate, neopentyl glycoldioctanoate, dibutyl sebacate, di-C₁₂₋₁₃ alkyl malate, dicetearyl dimerdilinoleate, dicetyl adipate, diisocetyl adipate, diisononyl adipate,diisopropyl dimerate, triisostearyl trilinoleate, octodecyl stearoylstearate, hexyl laurate, hexadecyl isostearate, hexydecyl laurate,hexyldecyl octanoate, hexyldecyl oleate, hexyldecyl palmitate,hexyldecyl stearate, isononyl isononanaote, isostearyl isononate,isohexyl neopentanoate, isohexadecyl stearate, isopropyl isostearate,n-propyl myristate, isopropyl myristate, n-propyl palmitate, isopropylpalmitate, hexacosanyl palmitate, lauryl lactate, octacosanyl palmitate,propylene glycol monolaurate, triacontanyl palmitate, dotriacontanylpalmitate, tetratriacontanyl palmitate, hexacosanyl stearate,octacosanyl stearate, triacontanyl stearate, dotriacontanyl stearate,stearyl lactate, stearyl octanoate, stearyl heptanoate, stearylstearate, tetratriacontanyl stearate, triarachidin, tributyl citrate,triisostearyl citrate, tri-C₁₂₋₁₃-alkyl citrate, tricaprylin,tricaprylyl citrate, tridecyl behenate, trioctyldodecyl citrate,tridecyl cocoate, tridecyl isononanoate, glyceryl monoricinoleate,2-octyldecyl palmitate, 2-octyldodecyl myristate or lactate,di(2-ethylhexyl)succinate, tocopheryl acetate, and the like.

Other suitable esters include those wherein R₅ comprises a polyglycol ofthe form H—(O—CHR*—CHR*)_(n)— wherein R* is independently selected fromhydrogen or straight chain alkyl, including methyl and ethyl, asexemplified by polyethylene glycol monolaurate.

Salicylates and benzoates are also contemplated to be useful esters inthe practice of the invention. Suitable salicylates and benzoatesinclude esters of salicylic acid or benzoic acid with an alcohol of theform R₆OH where R₆ is a linear, branched, or cyclic hydrocarbon group,optionally containing unsaturated bonds, and having from 1 to 30 carbonatoms, preferably from 6 to 22 carbon atoms, and more preferably from 12to 15 carbon atoms. Suitable salicylates include, for example, octylsalicylate and hexyldodecyl salicylate, and benzoate esters includingC₁₂₋₁₅ alkyl benzoate, isostearyl benzoate, hexyldecyl benzoate, benzylbenzoate, and the like.

Other suitable esters include, without limitation, polyglyceryldiisostearate/IPDI copolymer, triisostearoyl polyglyceryl-3 dimerdilinoleate, polyglycerol esters of fatty acids, and lanolin, to namebut a few.

The oil may also be a volatile or non-volatile silicone oil. Suitablesilicone oils include linear or cyclic silicones such as polyalkyl- orpolyarylsiloxanes, optionally comprising alkyl or alkoxy groups havingfrom 1 to 10 carbon atoms. Representative silicone oils include, forexample, caprylyl methicone, cyclomethicone, cyclopentasiloxanedecamethylcyclopentasiloxane, decamethyltetrasiloxane, diphenyldimethicone, dodecamethylcyclohexasiloxane, dodecamethylpentasiloxane,heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane,hexamethyldisiloxane, methicone, methyl-phenyl polysiloxane,octamethylcyclotetrasiloxane, octamethyltrisiloxane, perfluorononyldimethicone, polydimethylsiloxanes, and combinations thereof.

The silicone oil will typically, but not necessarily, have a viscosityof between about 5 and about 3,000 centistokes (cSt), preferably between50 and 1,000 cSt measured at 25° C.

In one embodiment, the silicone oil comprises phenyl groups, as is thecase for a preferred silicone oil methylphenylpolysiloxane, INCI namediphenyl dimethicone, commercially available from Shin Etsu Chemical Counder a variety of tradenames including F-5W, KF-54 and KF-56. Diphenyldimethicones have good organic compatibility and impart film-formingcharacteristics to the product. Further, the presence of phenyl groupsincreases the refractive index of the silicone oil, further contributingto the high gloss of product. In one embodiment, the silicone oil willhave a refractive index of at least 1.3, preferably at least 1.4, morepreferably at least 1.45, and more preferred still at least 1.5, whenmeasured at 25° C. Another suitable phenyl-functionalized silicone oilhas the INCI name phenyltrimethicone and is sold under the trade name“DC 556” by Dow Corning. DC 556 has a refractive index of about 1.46.

In one embodiment of the invention, the silicone oil is a fluorinatedsilicone, preferably a perfluorinated silicone (i.e., fluorosilicones).Fluorosilicones are advantageously both hydrophobic and oleophobic andthus advantageously contribute to a desirable slip and feel of theproduct. Fluorosilicones also impart long-wearing characteristics to thelip product. Fluorosilicones can be gelled with behenyl behenate andfurther incorporated into the ETPEA gel or can be incorporated intodimethicones, which can be further incorporated into the ETPEA gelnetwork. The preferred fluorosilicone is a fluorinated organofunctionalsilicone fluid having the INCI name perfluorononyl dimethicone.Perfluorononyl dimethicone is commercially available from PheonixChemical under the trade name Pecosil®.

The compositions may also comprise hydrocarbon oils. Exemplaryhydrocarbon oils are straight or branched chain paraffinic hydrocarbonshaving from 5 to 80 carbon atoms, preferably from 8 to 40 carbon atoms,and more preferably from 10 to 16 carbon atoms, including but notlimited to, pentane, hexane, heptane, octane, nonane, decane, undecane,dodecane, tetradecane, tridecane, and the like. Preferred hydrocarbonoils are highly branched aliphatic hydrocarbons, including C₈₋₉isoparaffins, C₉₋₁₁ isoparaffins, C₁₂ isoparaffin, and C₂₀₋₄₀isoparaffins and the like. Special mention may be made of theisoparaffins having the INCI names isohexadecane, isoeicosane, andisododecane.

Also suitable as hydrocarbon oils are polyalphaolefins, typically havinggreater than 20 carbon atoms, including C₂₄₋₂₈ olefins, C₃₀₋₄₅ olefins,hydrogenated polyisobutene, hydrogenated polydecene, polybutene, mineraloil, pentahydrosqualene, squalene, squalane, and the like. Thehydrocarbon oil may also comprise higher fatty alcohols, such as oleylalcohol, octyldodecanol, and the like.

Other suitable oils include without limitation castor oil, C₁₀₋₁₈triglycerides, caprylic/capric/triglycerides, coconut oil, corn oil,cottonseed oil, linseed oil, mink oil, olive oil, palm oil, illipebutter, rapeseed oil, soybean oil, sunflower seed oil, walnut oil,avocado oil, camellia oil, macadamia nut oil, turtle oil, mink oil,soybean oil, grape seed oil, sesame oil, maize oil, rapeseed oil,sunflower oil, cottonseed oil, jojoba oil, peanut oil, olive oil, andcombinations thereof.

Any one of the foregoing ester oils, silicone oils, and hydrocarbon oilsare contemplated to be useful in the practice of the invention.Accordingly, in one embodiment, the compositions comprise at least oneoil selected from the ester oils, silicone oils, and hydrocarbon oilsdescribed above. In another embodiment, the compositions comprise two ormore oils selected from the ester oils, silicone oils, and hydrocarbonoils described above. In yet another embodiment, the compositions willcomprise at least one ester, at least one silicone oil, and at least onehydrocarbon oil. Because the ester oils described herein function asemollients, it is preferred that the compositions comprise at least oneester oil, and will optionally comprise at least one additional oilselected from hydrocarbon oils, silicone oils, and combinations thereof.

The oils are preferably compatible with the ETPEA polymer such thatbelow the sol-gel transition temperature T_(gel) of the ETPEA polymer,the oils are incorporated into the gel matrix. ETPEA polymers can gelvariety of oils having a range of polarities, but the preferred ETPEApolymers typically, though not necessarily, are capable of optimalgellation only with low-polarity and non-polar oils. That is to say,firm gel structures, such as those required for self-supporting solidsand semi-solids capable of being formulated as lipsticks, are optimallyachieved with low-polarity and non-polar oils. The presence ofsubstantial amounts of higher polarity oils and solvents tends to weakenthe gel and are therefore less preferred, particularly where the gel isto be formulated as a self-supporting stick, such as a lipstick. Ofcourse, it is within the scope of the present invention to include polarcomponents, although high levels of such components may not be desirablefor all applications.

The ability of any given molecule to interact with any other moleculemay be expressed in terms of its Hansen Solubility Parameter accordingto the equation:

δ=(δ_(D) ²+δ_(P) ²+δ_(H) ²)^(1/2)

where δ_(D) is the dispersive or “nonpolar” parameter related to van derWaals interactions, δ_(p) is the polar parameter, related to the abilityof the molecule to form dipole-dipole interactions, and δ_(H), is aparameter related to the ability of the molecule to hydrogen bond.Typically, δ_(D) does not vary significantly between different speciesand therefore, as a useful approximation, can be ignored. The remainingparameters, δ_(p) and δ_(H), can be calculated based on the well-knownHildebrand parameters for any given molecule and plotted in atwo-dimensional “solubility space,” as described in Hansen, C. M.,“Hansen Solubility Parameter, A User's Handbook,” CRC Press, 1999, thedisclosure of which is hereby incorporated by reference herein.

Referring now to FIG. 2, the solvent space for the Hansen SolubilityParameters for a variety of solvents are shown. Each marker “⋄”represents the parameter pair (δ_(p),δ_(H)) for each solvent. Thesolvents range from relatively non-polar solvents capable of only weakhydrogen bonding interactions, such as toluene (δ_(p)=0.7, δ_(H)=1.0),to highly polar solvents capable of strong hydrogen bondinginteractions, such as diethylene glcol (δ_(p)=7.2, δ_(H)=10). Alsoincluded are relatively non-polar solvents capable of significanthydrogen bonding, including 2-ethyl-1-hexanol (δ_(p)=1.6, δ_(H)=5.8),and highly polar solvents with weak hydrogen bonding potential, such aspropylene carbonate (δ_(p)=8.8, δ_(H)=2.0)

The entire list of solvents shown in FIG. 2, along with the values(δ_(p),δ_(h)) are as follows: toluene (0.7, 1.0); xylene (mixed isomers)(0.9, 1.2); 2-ethyl-1-hexanol (1.6, 5.8); methyl t-butyl ether (1.7,2.5); n-butyl acetate (1.8, 3.1); iso-propyl palmitate (1.9, 1.8); DPMA(dipropylene glycol methyl ether acetate) (1.9, 4.0); cyclohexanol (2.0,6.6); tripropylene glycol (2.3, 7.6); dimethyl adipate (DBE) (2.4, 4.9);DPM (dipropylene glycol methyl ether) (2.6, 7.7); n-butyl alcohol (2.8,7.7); 2-ethylhexyl acetate (2.9, 5.9); iso-propyl alcohol (3.0, 8.0);methyl iso-butyl ketone (3.0, 2.0); cyclohexanone (3.1, 2.5); p-xylene(3.4, 1.0); ethyl lactate (3.7, 6.1); o-xylene (3.7, 0.0); diacetonealcohol (4.0, 5.3); isophorone (4.0, 3.6); hexylene glycol(2-methyl-2,2-pentanediol) (4.1, 8.7); hexanol (2-methyl-1-pentanol)(4.2, 6.2); ethyl alcohol (4.3, 9.5); methyl ethyl ketone (4.4, 2.5);EEP (ethyl-3-ethoxypropionate) (4.5, 4.6); PG (propylene glycol) (4.6,11.4); dipropylene glycol (DPG) (4.9, 9.0); ethylene glycol phenyl ether(EPH) (5.1, 7.8); EG (ethylene glycol) (5.4, 12.7);N,N-dimethylacetamide (5.6, 5.0); N-methyl-2-pyrrolidone (6.0, 3.5);triethylene glycol (6.1, 9.1); diethylene glcol (DEG) (7.2, 10.0); DMSO(8.0, 5.0); gamma-butyrolactone (8.1, 3.6); and propylene carbonate(8.8, 2.0). While the foregoing solvents adequately envelope the optimalsolubility space for the preferred ETPEA polymers of the invention,other useful ETPEA polymers may have gellation characteristics withsolvents of different polarities (i.e., with polar and highly polarmolecules). It is within the skill in the art to develop the solubilityspace over a range of polarities different from those provided hereinusing values of δ_(p) and δ_(h) which are readily available in theliterature for a variety of solvents or are readily calculated for anygiven molecule based on the Hildebrand parameters.

Along with the data points (δ_(p),δ_(h)) for the various solvents listedabove, FIG. 2 also shows the experimental results of combining the ETPEApolymer SYLVACLEAR® C75V with a representative number of solvents at a15% solids levels. The letter “G” is indicated by the tested solventswhich provided a firm, clear gel, the symbol “G_(h)” indicates that afirm gel was formed, but that the gel was hazy. The letter “M” indicatesthat a cloudy, white solid was formed. The letter “S” indicates that thepolymer was soluble in that solvent at the 15% by weight level, and thesymbol “S_(p)” indicates that a cloudy partial solution was formed. Theletter “I” indicates that the polymer was incompatible with the solvent.By overlaying the gellation characteristics of the ETPEA polymer withthe Hansen Solubility solvent space in this manner, the range of δ_(p)and δ_(h) values required for optimal gellation may be visualized andextended to any other solvent in accordance with the fundamentalprinciple of solubility/compatibility that “like dissolves like.” Forexample, it may be concluded that solvents, oils, and the like having aδ_(p) above about 5 tend to be incompatible with the particular ETPEApolymer SYLVACLEAR® C75V because N-methyl-2-pyrrolidone (δ_(p)=6.0) andethylene glycol phenyl ether (EPH) (δ_(p)=5.1) are each incompatiblewith the polymer, whereas all solvents in the range of δ_(p)=0 to 4.0and δ_(H)=0 to 4.0 formed gels at a level of 15% solids.

Thus, in one embodiment of the invention, the at least one ester oil,hydrocarbon oil, and/or silicone oil (or any additional solvents) willpreferably have a δ_(p) value below about 6, i.e., from 0 to about 6. Inother embodiments the ester oils, hydrocarbon oils, and/or silicone oilswill have a δ_(p) value less than or equal to about 5, or less than orequal to about 4.5, or less than or equal to about 4, or less than orequal to about 3.5. In other embodiments, the δ_(p) value of the esteroils, hydrocarbon oils, and/or silicone oils will be less than or equalto about 3, 2.5, or about 1. With regard to ester oils, δ_(p) istypically between 0 and about 4 (i.e., less than about 4), moretypically between about 0.5 and about 3, and, in some embodiments, willbe between about 1 and about 2.

The hydrogen bonding parameter δ_(h) of the at least one ester oil,hydrocarbon oil, and/or silicone oil (or any additional solvents) willtypically be below about 10, that is, between 0 and about 10. In otherembodiments, δ_(h) will be between 0 and about 9, between 0 and about 8,between 0 and about 7, between 0 and about 6. With regard to ester oils,δ_(H) is typically between 0 and about 5, more typically between about0.5 and about 4, and, in some embodiments, δ_(H) will be between about 1and about 2 or 3.

In other embodiments, the ester oil, hydrocarbon oil, and/or siliconeoil (or any additional solvents) will typically have a δ_(p) valuebetween 0 and about 6 and a δ_(h) value between 0 and about 10. Moretypically, the ester oils, hydrocarbon oils, and/or silicone oils willhave a δ_(p) value between 0 and about 5 and a δ_(h) value between 0 andabout 8 or about 9. More preferred ester oils, hydrocarbon oils, and/orsilicone oils will have a δ_(p) value between 0 and about 3, 3.5, 4 orabout 4.5 and a δ_(h) value between 0 and about 4, 5, 6 or about 7.

It should be understood, however, that the invention is not limited tothe use of oils having any particular solubility parameters providedthat the oil is compatible with the polymer such that syneresis islimited. Thus, for example, a high polarity oil or solvent may bepresent in small quantities even though at higher quantities it is notcapable of forming a gel with the ETPEA polymer. Preferably, oils andsolvents which are incompatible with the ETPEA polymer are present atless than about 10% by weight of the composition, preferably less thanabout 5% of the composition, and more preferably, less than about 2.5%of the composition. Thus, in one embodiment, the inventive compositionswill be substantially free of polar solvents, such as those having aδ_(p) value greater than about 6, greater than about 7, or greater thanabout 8, by which is meant that the compositions will have less thanabout 1% by weight of such solvents. Further, as shown in FIG. 2, somesolvents solubilize the polymer at 15% by weight as indicated by thesymbols “S” and “S_(p)”. This does not mean that such solvents are notuseful in the practice of the invention, but rather that more ETPEApolymer may be required in the formulation in order to form a suitablegel network. While the preferred compositions will typically comprise15% ETPEA polymer or less, other embodiments will have, for example, upto about 20%, 25%, 30%, 35%, or even about 40% by weight ETPEA polymerand therefore may provide suitable gels with such solvents. Accordingly,the values of δ_(p) and δ_(h) described herein are particularlyappropriate for the preferred compositions which will comprise betweenabout 0.1 and about 15% by weight of ETPEA polymer.

The oil components will typically comprise, individually orcollectively, from about 0.1% to about 90% by weight of the composition.More typically, the collective weight of all oil components (ester oils,hydrocarbon oils, and silicone oils) will constitute from about 5%, 10%,15%, 20%, 25%, or 30% to about 65%, 70%, 75% or 80% of the total weightof the composition. In one exemplary embodiment, the oils collectivelycomprise between about 30% and about 70%, preferably between about 40%and about 60% by weight, of the total composition, particularly wherethe ETPEA polymer comprises between about 0.5 and about 12% by weight ofthe total composition. Excellent results have been obtained wherein thecollective content of ester oils is from about 30-60% by weight, orabout 40-50% by weight.

The compositions of the invention will optionally comprise one or morecolorants, including pigments, dyes, lakes, and the like. As usedherein, the term “pigment” is intended to include white pigments such astitanium dioxide, zinc oxide, mica, pearls, and the like. The collectiveweight of all colorants, when present, will usually range from about0.1% up to about 30% of the composition, typically from about 1% toabout 20%, preferably from about 2.5 to about 15%, and, in a preferredembodiment, from about 5 to about 10%. It has surprisingly been foundthat high levels of pigments, particularly mica and pearls, do notsignificantly diminish the gloss of the lip products according to theinvention. In some embodiments of the invention, the 85 degree glossvalue of the lip products, in the presence of between about 0.1-15%,1-10%, 2-10%, 4-10%, 6-10%, or 8-10% by weight pearl and/or micacomponents, will be within 20%, preferably within 15%, more preferablywithin 10%, and more preferred still, within 5% of the 85 degree glossvalue of an otherwise identical composition containing no pearl and/ormica components. The 85 degree gloss value will in some embodiments, beat least 45, at least 50, at least 55, or at least 60. More typically,the 85 degree gloss will be at least 65, and preferably at least 70,even in the presence of pearl and/or mica components, including forexample from at least 1%, at least 2%, at least 4%, at least 6%, atleast 8%, or even at least 10% by weight pearl and/or mica components.Preferred lipsticks will exhibit an 85 degree gloss value of 75 orhigher, and preferably 80 or higher, across a pearl and mica loadingrange of 0-15% by weight.

The compositions may also comprise one or more particulates, includingwithout limitation mica, talc, bismuth oxychloride, bentonite, nylon,silica, acrylates copolymer, teflon, spherical silica, and the like. Itis believed that similar results will be obtained with any particulatematerial. That is to say, the gloss of the inventive compositions willnot be substantially diminished by particulate levels in the range of0-10% by weight. In this context “substantially diminished” is intendedto mean that the attenuation of gloss will be less than about 20%,preferably less than 15%, more preferably less than 10%, and morepreferred still, less than 5% of the 85 degree gloss value of anotherwise identical composition in the absence of the particulatematerial and will preferably be at least 75 or higher, and preferably 80or higher.

In one preferred aspect of the invention, the compositions are capableof delivering high gloss when applied to the lips. By the term “highgloss” is meant an 85 degree gloss value greater than about 70,typically greater than about 75, and preferably greater than about 80.It has surprisingly been found that lipstick products prepared with theinventive compositions can exhibit a gloss comparable to or even greaterthan conventional wax-free oil-based lip gloss products. Thus, in someembodiments, the 85 degree gloss value of a lipstick comprising theinventive compositions will be greater than about 82, 84, 86, 88, oreven 90. It is contemplated that 85 degree gloss values of 95 or evenhigher may be achieved by the inventive lip products.

In embodiments where the compositions are to be formulated as aself-supporting stick, the compositions will have a hardness above 40 g(grams). Typically, the compositions will have a hardness above about 50g and more typically above about 60 g. Preferably, the compositions willhave a hardness above about 70 g, 80 g, 90 g or 100 g. In someembodiments, the hardness of the compositions will be at least 120 g,140 g, 160 g, 180 g, or 200 g. In other embodiments, the compositionswill have a hardness of at least 250 g, 300 g, 350 g, or 400 g. However,in the broadest aspects, the invention is not strictly limited tocompositions having any particular hardness. The compositions arecontemplated to be useful even when provided as weak gels and the like.Surprisingly, it has been found that even relatively hard sticks, forexample those having a hardness between about 200 g and about 300 g,exhibit excellent “pay off” such that upon application to the lips anacceptable amount of product is transferred to the lips. The assessmentof pay off is well-known in the art and may be quantified, for example,by expert panel testing on a scale from 1 to 10, etc.

In one aspect, the inventive compositions provide a unique rheology notobtainable with conventional wax-based lipsticks. The rheology ischaracterized by a perception that the lipstick retains a freshlyapplied feeling on the lips over a long period of wear, meaning that thefeeling of the lipstick remains unctuous over that time. Conventionalwax-based lipsticks are known to initially feel oily when applied butrapidly become dry, particularly after the wearer rubs their lipstogether and the like. This effect is believed to arise due to thebreakdown of the wax structure brought about by shear from rubbing thelips, etc. This effect may be described as the shear-induced breakdownof the wax matrix.

In contrast to conventional lipsticks, the compositions of the inventiondo not exhibit shear-induced breakdown of the gel structure, or exhibitreduced shear-induced breakdown of the gel structure as compared towax-based lipsticks. The result is that the lipsticks of the inventionretain a long wearing oily feeling on the lips. This effect may byquantified in terms of the viscosity of the composition over repeatedshear cycles. Typically, the inventive compositions have rheologycharacterized by a viscosity at a given shear rate which remainssubstantially constant over repeated shear cycles, particularly withshear rates between about 1 and about 10 sec⁻¹ typically encounteredduring wear. That is to say, the gel network remains elastic such thatshear does not induce degradation of the network. In contrast, the waxbase of conventional lipsticks undergoes shear induced degradation suchthat the viscosity of the wax decreases with repeated shear cycles. By“relatively constant” is mean that, while some variance in theviscosity/shear rates profiles is tolerable over multiple shear cycles,the second shear cycle should produce a viscosity falling within ±3 SD(standard deviation) of the viscosity measured in a first shear cycle ateach shear rate between about 1 and about 10 sec⁻¹. Preferably, theviscosity measured in a second shear cycle will be within ±2 SD, morepreferably ±1 SD of the viscosity measured in a first shear cycle ateach shear rate between about 1 and about 10 sec⁻¹.

In some embodiments, the viscosity during a second and third shear cyclewill be within ±3 SD, ±2 SD, or ±1 SD of the viscosity measured in afirst shear cycle at each shear rate between about 1 and about 10 sec⁻¹.

In some embodiments, the viscosity of the inventive compositions duringa second shear cycle, and preferably during a third shear cycle, will begreater than about 50, 75, or about 100 Pa·sec at every shear ratebetween about 1 and about 5 sec⁻¹ and/or the viscosity during a secondshear cycle, and preferably during a third shear cycle, will be greaterthan about 5, 7.5 or about 10 Pa·sec at every shear rate between about10 and about 50 sec⁻¹ and/or the viscosity of the inventive compositionsduring a second shear cycle, and preferably during a third shear cycle,will be greater than about 0.5, 0.75, or about 1 Pa·sec at shear ratesbetween about 100 and about 500 sec⁻¹ wherein said second shear cyclesfollows a first shear cycle covering shear rates from about 1 to about1,000 sec⁻¹.

In one embodiment, the composition for imparting an unctuous film to thelips comprises:

-   -   (a) from about 0.1 to about 40% by weight of an ester terminated        poly(ester-amide) polymer having an average molecular weight        between about 3,000 and about 7,500 Daltons and being capable of        forming a gel with low-polarity and nonpolar oils at or below a        sol-gel transition temperature T_(gel) wherein T_(gel) is above        body temperature;    -   (b) from about 0.1 to about 20% by weight of a first wax        component comprising one or more waxes having a melting point        above T_(gel);    -   (c) from about 0.1 to about 20% by weight of a second wax        component comprising one or more waxes having a melting point at        or below T_(gel); and    -   (e) one or more low-polarity or nonpolar oils capable of forming        a gel with said ester terminated poly(ester-amide) polymer at or        below said sol-gel transition temperature T_(gel); wherein said        one or more low-polarity or nonpolar oils are selected from the        group consisting of esters, hydrocarbons, and silicone-based        oils;        wherein the composition is characterized by a viscosity measured        during a second shear cycle that is within ±20% of the viscosity        measured during a first shear cycle at every shear rate between        about 1 and about 10 sec⁻¹, wherein the first and the second        shear cycles are identical and comprise increasing shear rates        from about 1 to about 1,000 sec⁻¹.

In one variant, the second shear cycle is within ±10% of the viscositymeasured during the first shear cycle at every shear rate between about1 and about 10 sec⁻¹. In another variant, the viscosity measured duringthe second shear cycle is within ±5% of the viscosity measured duringthe first shear cycle at every shear rate between about 1 and about 10sec⁻¹.

In another embodiment, the compositions are characterized by a viscositymeasured during the second shear cycle that is within ±20% of theviscosity measured during the first shear cycle at every shear ratebetween about 10 and about 100 sec⁻¹. In one variant according to thisembodiment, the viscosity measure during the second shear cycle iswithin ±10% of the viscosity measured during the first shear cycle atevery shear rate between about 10 and about 100 sec⁻¹. In anothervariant, the viscosity measured during the second shear cycle is within±5% of the viscosity measured during the first shear cycle at everyshear rate between about 10 and about 100 sec⁻¹.

In yet another embodiment, the viscosity measured during the secondshear cycle is within ±20% of the viscosity measured during the firstshear cycle at every shear rate between about 1 and about 100 sec⁻¹. Inone variant according to this embodiment, the viscosity measured duringthe second shear cycle is within ±10% of the viscosity measured duringthe first shear cycle at every shear rate between about 1 and about 100sec⁻¹. Preferably, the viscosity measured during the second shear cycleis within ±5% of the viscosity measured during the first shear cycle atevery shear rate between about 1 and about 100 sec⁻¹.

The compositions for imparting an unctuous film to the lips may befurther characterized by a viscosity greater than about 50, 75, or about100 Pa·sec at a shear rate of about 1 sec⁻¹ as measured during a firstshear cycle. Preferably, the compositions are characterized by aviscosity greater than about 50, 75, or about 100 Pa·sec at a shear rateof about 1 sec⁻¹ as measured during both the first and second shearcycles. In one variant, the compositions are characterized by aviscosity greater than about 50, 75, or about 100 Pa·sec at shear ratesfrom about 1 to about 5 sec⁻¹ as measured during the first shear cycle,and preferably during the first and second shear cycles.

Preferred compositions will be characterized by a viscosity greater thanabout 5, 7.5, or about 10 Pa·sec at a shear rate of about 10 sec⁻¹ asmeasured during said first shear cycle and preferably will have aviscosity greater than about 5, 7.5, or about 10 Pa·sec at a shear rateof about 10 sec⁻¹ as measured during the first and second shear cycles.More preferred compositions will be characterized by a viscosity greaterthan about 5, 7.5, or about 10 Pa·sec at a shear rate from about 10 toabout 50 sec⁻¹ as measured during the first shear cycle, and preferablyas measured during both the first and second shear cycles.

In other embodiments, the compositions will further be characterized bya viscosity greater than about 0.5, 0.75, or about 1 Pa·sec at a shearrate of about 100 sec⁻¹ as measured during said first shear cycle andpreferably will have a viscosity greater than about 0.5, 0.75, or about1 Pa·sec at a shear rate of about 100 sec⁻¹ as measured during the firstand the second shear cycles.

Alternatively, the rheology may be quantified by expert panel testing ona 0-10 scale on the basis of parameters such as slip, feel, oiliness,moisture, and/or dryness over a period of wear, including for example 15minutes, 30 minutes, 45 minutes, and 1 hour.

It will be understood that the selection of and amounts of ETPEApolymer, wax, oil, silicone T-resin, etc., described herein are equallyapplicable to both the compositions for imparting high gloss andcompositions having the improved rheology described herein. In preferredaspects of the invention, the lip compositions will exhibit both highgloss and improved rheology.

The compositions of the invention may further comprise one or more filmformers and polymers. Fluorinated polymers, such as those having theINCI name polyperfluoromethylisopropyl ether, are particularly useful tomodify slip and feel of the composition. Preferred fluorinated polymersare supplied by Solvey Solexis under the trade name FOMBLINHC. Sucroseacetate isobutyrate (INCI) supplied by Eastman Chemical and glycerolrosinate (INCI) sold under the trade name SylvaGum RE 85K by ArizonaChemical are preferred film formers.

Various fillers may be incorporated into the compositions. Suitablefillers include without limitation silica, treated silica, talc, zincstearate, mica, kaolin, Nylon powders such as Orgasol™, polyethylenepowder, Teflon™, starch, boron nitride, copolymer microspheres such asExpancel™ (Nobel Industries), Polytrap™ (Dow Corning) and silicone resinmicrobeads (Tospearl™ from Toshiba), and the like.

Additional pigment/powder fillers include, but are not limited to,inorganic powders such as gums, chalk, Fuller's earth, kaolin, sericite,muscovite, phlogopite, synthetic mica, lepidolite, biotite, lithia mica,vermiculite, aluminum silicate, starch, smectite clays, alkyl and/ortrialkyl aryl ammonium smectites, chemically modified magnesium aluminumsilicate, organically modified montmorillonite clay, hydrated aluminumsilicate, fumed aluminum starch octenyl succinate barium silicate,calcium silicate, magnesium silicate, strontium silicate, metaltungstate, magnesium, silica alumina, zeolite, barium sulfate, calcinedcalcium sulfate (calcined gypsum), calcium phosphate, fluorine apatite,hydroxyapatite, ceramic powder, metallic soap (zinc stearate, magnesiumstearate, zinc myristate, calcium palmitate, and aluminum stearate),colloidal silicone dioxide, and boron nitride; organic powder such aspolyamide resin powder (nylon powder), cyclodextrin, methylpolymethacrylate powder, copolymer powder of styrene and acrylic acid,benzoguanamine resin powder, poly(ethylene tetrafluoride) powder, andcarboxyvinyl polymer, cellulose powder such as hydroxyethyl celluloseand sodium carboxymethyl cellulose, ethylene glycol monostearate;inorganic white pigments such as magnesium oxide. Other useful powdersare disclosed in U.S. Pat. No. 5,688,831, the disclosure of which ishereby incorporated by reference.

The compositions of the invention will typically comprise one or morecoloring agents. Suitable coloring agents, including pigments, lakes,and dyes, are well known in the art and are disclosed in the C.T.F.A.Cosmetic Ingredient Handbook, First Edition, 1988, the contents or whichare hereby incorporated by reference. Organic pigments include, forexample, FD&C dyes, D&C dyes, including D&C Red, Nos. 2, 5, 6, 7, 10,11, 12, 13, 30 and 34, D&C Yellow No. 5, Blue No. 1, Violet No. 2.Exemplary inorganic pigments include, but are not limited to, metaloxides and metal hydroxides such as magnesium oxide, magnesiumhydroxide, calcium oxide, calcium hydroxides, aluminum oxide, aluminumhydroxide, iron oxides (α-Fe₂O₃, y-Fe₂O₃, Fe₃O₄, FeO), red iron oxide,yellow iron oxide, black iron oxide, iron hydroxides, titanium dioxide,titanium lower oxides, zirconium oxides, chromium oxides, chromiumhydroxides, manganese oxides, cobalt oxides, cerium oxides, nickeloxides and zinc oxides and composite oxides and composite hydroxidessuch as iron titanate, cobalt titanate and cobalt aluminate. Othersuitable colorants include ultramarine blue (i.e., sodium aluminumsilicate containing sulfur), Prussian blue, manganese violet, bismuthoxychloride, talc, mica, sericite, magnesium carbonate, calciumcarbonate, magnesium silicate, aluminum magnesium silicate, silica,titanated mica, iron oxide titanated mica, bismuth oxychloride, and thelike. The colorants may be surface modified with, for example,fluoropolymers, to adjust one or more characteristics of the colorant asdescribed in, for example, U.S. Pat. Nos. 6,471,950, 5,482,547, and4,832,944, the contents of which are hereby incorporated by reference.Suitable pearling pigments include without limitation bismuthoxychloride, guanine and titanium composite materials containing, as atitanium component, titanium dioxide, titanium lower oxides or titaniumoxynitride, as disclosed in U.S. Pat. No. 5,340,569, the contents ofwhich are hereby incorporated by reference. The composition may alsocontain a cosmetically acceptable glitter, including metallic particlesor solid organic particles such as those described in U.S. Patent Pub.2002/0006422, the contents of which are hereby incorporated byreference.

The compositions of the invention may further comprise a cosmeticvehicle, including without limitation linear and cyclic volatilesilicones, including those available from the Dow Corning Corporationunder the tradenames Dow Corning 244, 245, 344, and 200 fluids. Thesefluids include octamethylcyclotetrasiloxane,decamethylcyclopentasiloxane, hexamethyldisiloxane, or mixtures thereof.Also contemplated to be useful are the branched volatile siliconescommercially available from Shinetsu. Water soluble vehicles such asbutylene glycol, propylene glycol, polyglycerol diisostearate,dimethylsiloxane/glycol copolymer, isopropyl myristate, triisostearylcitrate, and the like may also be present. The weight percentage of thevehicle, excluding ester oils, silicone oils, and hydrocarbon oilscapable of forming a gel with the ETPEA polymer, will typically be lessthan about 10% by weight, more typically less than about 5% by weight,and preferably less than about 1% by weight of the composition.

The compositions of the invention may optionally comprise other activeand inactive ingredients typically associated with cosmetic and personalcare products, including, but not limited to, excipients, fillers,emulsifying agents, antioxidants, surfactants, film formers, chelatingagents, gelling agents, thickeners, emollients, humectants,moisturizers, vitamins, minerals, viscosity and/or rheology modifiers,sunscreens, keratolytics, depigmenting agents, retinoids, hormonalcompounds, alpha-hydroxy acids, alpha-keto acids, anti-mycobacterialagents, antifungal agents, antimicrobials, antivirals, analgesics,lipidic compounds, anti-allergenic agents, H1 or H2 antihistamines,anti-inflammatory agents, anti-irritants, antineoplastics, immune systemboosting agents, immune system suppressing agents, anti-acne agents,anesthetics, antiseptics, insect repellents, skin cooling compounds,skin protectants, skin penetration enhancers, exfollients, lubricants,fragrances, colorants, staining agents, depigmenting agents,hypopigmenting agents, preservatives, stabilizers, pharmaceuticalagents, photostabilizing agents, and mixtures thereof. In addition tothe foregoing, the compositions of the invention may contain any othercompound for the treatment of skin disorders.

Example I High Gloss Lipstick

Table 2 provides a high gloss lipstick comprising the ETPEA gellantSylvaclear® C75V (Arizona Chemicals), a high melting point wax component(microcrystalline petroleum wax and linear polyethylene), a low meltingpoint wax component (ozokerite), a high refractive index siliconeT-resin co-gellant, and a variety of low-polarity ester oils.

TABLE 2 Component Function Weight % Microcrystalline Petroleum Wax Firstwax component 0.6 Polyethylene-Linear Pl First wax component 5.85Ozokerite 170-D Second wax component 1.55 Sylvaclear ® C75V ETPEAgellant 1.0 Polyphenylsilsesquioxane Silicone T-resin gellant 5.9Silica-High Oil Absorbing Particulate based gelling 2.0 agentTriisostearoyl Polyglyceryl-3 Esters 9.0 Dimer Dilinoleate DiisopropylDimerate Esters 2.5 Triisostearyl Trilinoleate Esters 13.6 C12-15Alcohols Benzoate Esters 2.0 Octyldodecyl Stearoyl Stearate Esters 6.15Diisostearyl Fumarate Esters 15.5 Polyglyceryl-2 Diisostearate/IPDIEsters 3.5 Copolymer Sucrose Acetate Isobutyrate Film former 2.5VP/Eicosene Copolymer Film former 1.65 PVP/Hexadecene Copolymer Filmformer 4.0 Lanolin-Low Odor Film former 6.5 Glyceryl Rosinate-Food GradeFilm former 0.5 Ethylhexyl-Methoxycinnamate Sunscreen 7.0 OctocryleneSunscreen 2.0 Caprylyl Glycol Preservative 0.5 Sucralose Sweetener 0.02Colorants Colorants 6.03 Fragrance Fragrance 0.15

The product was prepared by mixing the ingredients of Table 2 above 100°until all of the waxy components melted. The molten mixture was pouredinto a mold and allowed to solidify. The resulting product was aself-supporting solid having physical stiffness comparable to aconventional lip stick.

A glossmeter was used to measure the specular reflection from a film ofthe lipstick at 85 degrees. The average of multiple measurements was 87which far exceeds the gloss of conventional wax-based lipsticks and,surprisingly exceeds the gloss of some liquid lip gloss products andtwo-coat high gloss lip products. FIG. 1 compares the 85 degree gloss ofthe lipstick of Table 2 with the several conventional lip products. InFIG. 1, “A” represents the lipstick of Table 2, and the remaining lipproducts are as follows: B=Glazewear™ liquid lip gloss (Avon Products);C=Color Rich™ (shade 1) (Avon Products); D=Color Rich™ (shade 2) (AvonProducts); E=Butter Shine™ (Clinique); F=Ultra Color Rich™ (shade 1)(Avon Products); G=Ultra Color Rich™ (Shade 2) (Avon Products);H=Moisture Extreme™ (Maybelline); I=Shine Supreme™ (Avon Products);J=Colour Riche™ (L'Oreal); K=Wet Shine™ (shade 1) (Maybelline); L=WetShine™ (shade 2) (Maybelline); M=Brilliant Moisture™ (shade 1) (AvonProducts); N=Brilliant Moisture™ (shade 2) (Avon Products); and Orepresents a two-step lip product of the type involving a transparent,high gloss top coat.

Notably, the 85 degree gloss value of the lipstick of Table 2outperforms not only the conventional wax-based lipsticks (C—N), butalso the liquid lip gloss (B) and the two step lip product (O), whichheretofore represented the state of the art in delivering high shine.

Example II

The effect of increasing pearl and mica content on the 85 degree glossof lip products was investigated. Four samples of the inventivelipsticks having pearl and mica contents ranging from 0% to 10% byweight were prepared. The formulations for the four samples are providedin Table 3.

TABLE 3 Weight % Weight % Weight % Weight % Component 0.6 0.6 0.6 0.6Microcrystalline Petroleum Wax 5.85 5.85 5.85 5.85 Polyethylene-LinearPl 1.55 1.55 1.55 1.55 Ozokerite 170-D 1.0 1.0 1.0 1.0 Sylvaclear ® C75V5.9 5.9 5.9 5.9 Polyphenylsilsesquioxane 2.0 2 1.5 2.0 Silica-High OilAbsorbing 9.0 9.0 9.0 9.0 Triisostearoyl Polyglyceryl-3 DimerDilinoleate 2.5 2.5 2.5 2.5 Diisopropyl Dimerate 13.6 13.6 13.6 9.38Triisostearyl Trilinoleate 2.0 2.0 2.0 2.0 C12-15 Alcohols Benzoate 6.156.15 6.15 6.15 Octyldodecyl Stearoyl Stearate 15.5 15.5 17 10.5Diisostearyl Fumarate 3.5 3.5 3.0 3.5 Polyglyceryl- 2 Diisostearate/IPDICopolymer 2.5 2.5 2.0 2.5 Sucrose Acetate Isobutyrate 1.65 1.65 1.651.65 VP/Eicosene Copolymer 4.0 4.0 4.0 4.0 PVP/Hexadecene Copolymer 6.56.5 6.5 6.5 Lanolin-Low Odor 0.5 0.5 0.5 0.5 Glyceryl Rosinate- FoodGrade 7.0 7.0 7.0 7.0 Ethylhexyl- Methoxycinnamate 2.0 2.0 2.0 2.0Octocrylene 0.5 0.5 0.5 0.5 Caprylyl Glycol 0.02 0.02 0.02 0.02Sucralose 6.03 2.78 0.88 5.25 Colorants — 3.25 5.15 10 Pearls and Mica0.15 0.15 0.15 0.15 Fragrance

The gloss of the inventive lipsticks were compared against aconventional wax-based lipstick having pearl and mica contents rangingfrom 2% to about 10% by weight, as shown in Table 4.

TABLE 4 Weight % Sample 1 Sample 2 Sample 3 Sample 4 Component 4.60 4.604.60 4.60 micro wax white 2.75 2.75 2.75 2.75 polyethylene-linear pl5.00 5.00 5.00 5.00 ozokerite 170-D 12.00 12.00 12.00 12.00 diglyceryldiisostearate 20.00 20.00 20.00 20.00 glyceryl triacetyl hydroxystearate2.00 2.00 2.00 2.00 polyglycerol diisostearate 16.30 16.30 16.30 16.30triisostearyl trilinoleate 1.60 1.60 1.60 1.60 phenyl trimethicone/bentone gel 8.80 8.80 8.80 8.80 hydrogenated polyisobutene 8.00 8.008.00 8.00 lanolin acetate 5.50 5.50 5.50 5.50 polybutene 0.12 0.12 0.120.12 acrylate copolymer E0603 1.75 1.75 1.75 1.75 polyethylene 1-20microns 0.50 0.50 0.50 0.50 caprylyl glycol 8.96 7.0 5.08 0.6 colorants2.00 3.96 5.88 10.36 pearls and mica 0.12 0.12 0.12 0.12 fragrance

FIG. 3 compares the 85° gloss for the four ETPEA gel-based lipsticks(indicated by the data points “Δ”) and the four samples of wax-basedlipstick (indicated by the data points “□”) at the various pearl andmica loadings. Clearly evident is the fact that the gloss does notsignificantly diminish over the 0-10% by weight range for the ETPEAgel-based formulations of the invention, and in all cases remains quitehigh, i.e., greater than 80, whereas in the convention wax-basedlipsticks the 85 degree gloss diminishes substantially (greater thanabout 50%) over mica and pearl loadings of 2 to about 10% by weight. Thedata corresponding to FIG. 3 is shown below in Table 5.

TABLE 5 Pearl & Mica (wt. %) 85° Gloss gel base (Δ) 0 87 1.16 81.85 3.2582 5.15 80.3 10 83.85 wax base (□) 2 54 3.96 37 5.88 27.5 10.36 22

Further, it is evident that the conventional wax-based formulationsprovide inferior gloss as compared to the inventive lipsticks over theentire range of pearl and mica loading. Thus, one surprising advantageof the compositions of the invention is that they permit the formulatorto include high levels of pearling agents without sacrificing shine. By“high levels” is meant at least 5%, preferably at least 7.5%, and morepreferably at least 10% or at least 12% by weight.

Example III

The formulation parameters effecting the hardness of the ETPEA gel wereinvestigated using the various lipstick formulation shown in Table 6.The hardness of each lipstick was measured on a Texture Analyzer ModelQTS-25 equipped with a 4 mm stainless steel probe (TA-24). As the datain Table 6 illustrates, the firmness of the gel is the result of acomplex interaction between the ETPEA, wax, silicone T-resin, oil, andpigments/pearl contents of the lipstick. In each case, the formulationsin Table 6 are expressed as weight percent of the entire formulation sothat the ester oil content varies somewhat between each sample toaccommodate the increase or decrease in the ETPEA, silicone T-resin,wax, and pigment/pearl components. Nevertheless, general trends areobserved for the effect of varying the ETPEA, wax, silicone T-resin,oil, and pigments/pearl contents of the lipstick.

TABLE 6 Sample Number: 1 2 3 4 5 6 7 8 9 10 Component Weight %Microcrystalline Petroleum Wax 0.60 0.60 0.60 0.70 0.55 0.60 0.60 0.430.38 0.53 Polyethylene-Linear Pl 5.85 5.85 5.85 7.00 5.00 5.85 5.85 4.183.67 5.13 Ozokerite 170-D 1.55 1.55 1.55 1.90 1.30 1.55 1.55 1.11 0.971.36 Sylvaclear ® C75V 1.00 1.00 5.90 5.90 5.90 12.00 4.90 28.57 25.060.88 Polyphenylsilsesquioxane 5.90 5.90 5.90 5.90 5.90 2.00 2.00 4.2115.98 17.54 Silica-High Oil Absorbing 2.00 2.00 2.00 2.00 2.00 2.00 2.001.43 1.25 1.75 Triisostearoyl Polyglyceryl-3 Dimer Dilinoleate 9.00 9.009.00 9.00 9.00 9.00 9.00 6.43 5.64 7.89 Diisopropyl Dimerate 2.50 2.502.50 2.50 2.50 2.50 2.50 1.79 1.57 2.19 Triisostearyl Trilinoleate 9.3813.60 10.65 9.05 11.00 10.00 13.60 9.71 8.52 11.93 C12-15 AlcoholsBenzoate 2.00 2.00 2.00 2.00 2.00 2.00 2.00 1.43 1.25 1.75 OctyldodecylStearoyl Stearate 6.15 6.15 6.15 6.15 6.15 6.15 6.15 4.39 3.85 5.39Diisostearyl Fumarate 10.50 15.50 13.55 13.55 13.55 12.00 15.50 11.079.71 13.60 Polyglyceryl-2 Diisostearate/IPDI Copolymer 3.50 3.50 3.503.50 3.50 3.50 3.50 2.50 2.19 3.07 Sucrose Acetate Isobutyrate 2.50 2.502.50 2.50 2.50 2.50 2.50 1.79 1.57 2.19 VP/Eicosene Copolymer 1.65 1.651.65 1.65 1.65 1.65 1.65 1.18 1.03 1.45 PVP/Hexadecene Copolymer 4.004.00 4.00 4.00 4.00 4.00 4.00 2.86 2.51 3.51 Lanolin-Low Odor 6.50 6.506.50 6.50 6.50 6.50 6.50 4.64 4.07 5.70 Glyceryl Rosinate-Food Grade0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.36 0.31 0.44Ethylhexyl-Methoxycinnamate 7.00 7.00 7.00 7.00 7.00 7.00 7.00 5.00 4.396.14 Octocrylene 2.00 2.00 2.00 2.00 2.00 2.00 2.00 1.43 1.25 1.75Caprylyl Glycol 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.36 0.31 0.44Sucralose 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.01 0.01 0.02 Pigments &Pearls 15.25 6.03 6.03 6.03 6.03 6.03 6.03 4.31 3.78 5.29 Fragrance 0.150.15 0.15 0.15 0.15 0.15 0.15 0.11 0.09 0.13 Hardness (grams) 204 201 62174 117 43 109 271 272 413 (±1.25) (±5.44) (±1.63) (±1.25) (±3.27)(±2.62) (±1.40) (±1.41) (±2.16) (±5.56)

For example, Samples 1 and 2 contain the identical amounts of wax, ETPEApolymer, and silicone T-resin, but differ primarily in the weightpercentage of pigments and pearl (15.25% vs. 6.03%), however nosignificant loss of hardness was observed (204 g vs. 201 g).

Samples 2 and 3 contain identical weight percentages of wax, siliconeT-resin, and pigments/pearls, but differ in amount of ETPA gellant from1% (Sample 2) to 5.9% (Sample 3). The corresponding hardness is seen todecrease with increasing ETPEA polymer from 201 g at 1% to 62 g at 5.9%ETPEA. The latter hardness is only slightly above the hardness threshold(40 g) for making a suitable self-supporting stick. The loss of hardnessin Sample 3 is likely the consequence of increasing the ratio of ETPEApolymer to ester oils from about 1:52 in Sample 2 to about 1:8 in Sample3. Thus, it may be said that the preferred gels will have a weight ratioof ETPEA polymer to ester oils of less than 1:8, typically less than1:10, preferably less than 1:15, more preferably less than 1:20, andmore preferred still less than 1:30, particularly in embodiments havinga silicone T-resin co-gellant level of about 5.5 to about 6.5% byweight, including 5.9% by weight. In exemplary embodiments, the ratio ofETPEA polymer to ester oils will be less than 1:40 or less than 1:50. Ofcourse the ratio of ETPA polymer to oil will be limited, at the low end,by the point at which the amount of oil is so large that it solubilizesthe polymer rather than forms a gel. At the high end of the ratio, gelsof suitable firmness have been obtained with a weight ratio of ETPEApolymer to ester oils of about 1:1.3 or less (Sample 8 and 9) providedthat suitable adjustments to the levels of other functional componentsare made.

Samples 6 and 7 show the effect of increasing ETPEA content informulations having a lower silicone T-resin content than in Samples 2and 3. In Samples 6 and 7, the silicone T-resin content is 2% by weightas compared to 5.9% by weight in Samples 2 and 3. As with Samples 2 and3, it was similarly found that the firmness of the gel decreases withincreasing ETPEA content from 109 g at 4.9% (Sample 7) to 43 g at 12%(Sample 6). The latter hardness value being only marginally above thehardness threshold of 40 g for making self-supporting solid sticks. Theweight ratio ETPEA polymer to ester oils is about 1:3.75 in Sample 6 andabout 1:10 in Sample 7. Again, even at a low silicone T-resin content of2% by weight, a 1:10 ratio of ETPEA polymer to ester oils was found toprovide suitable gels. At a ratio of 1:3.75 the gel exhibited a lessdesirable firmness, although it was above the 40 g hardness cut-off.Thus, in embodiments containing low amounts of silicone T-resin, i.e.,less than about 5% by weight, and particularly less than about 3% byweight, suitable gels are obtained with a ratio of ETPEA to ester oilsof less than about 1:3.75, more typically less than about 1:4 andpreferably, about 1:10 or less.

Between Samples 4 and 5 it may generally be observed that the firmnessof the gel improves with increasing wax content at the same weightpercentages of ETPEA, silicone T-resin, and pigment/pearls. Thesesamples range in total wax content from 6.85% to 9.6% with acorresponding increase in hardness from 117 g to 174 g. This result isnot surprising as the waxy components are known to provide stiffness intraditional wax-based lipsticks. However, in the preferred practice ofthe invention, it is desirable not to exceed 12% by weight wax contentas the waxes can mute the gloss of the product.

Sample 10 provides a very firm gel (413 g) made with a very low, 0.88%by weight, content of ETPEA polymer. The ratio of ETPEA gellant to esteroils is than 1:50. The remarkable firmness of this gel results in partfrom the high content of silicone T-resin gellant.

As evident from Table 6, gels of suitable hardness can be obtained overa wide range of ETPEA, wax, oil, silicone T-resin, and pigment/pearlcontents. In embodiments where the compositions are to be formulated asa self-supporting stick, the compositions will have a hardness above 40g. Typically, the compositions will have a hardness above about 50 g andmore typically above about 60 g. Preferably, the compositions will havea hardness above about 70 g, 80 g, 90 g or 100 g. In some embodiments,the hardness of the compositions will be at least 120 g, 140 g, 160 g,180 g, or 200 g. In other embodiments, the compositions will have ahardness of at least 250 g, 300 g, 350 g, or 400 g.

Example IV

In one aspect, the inventive compositions provide a unique rheology notobtainable with conventional wax-based lipsticks. The rheology ischaracterized by a perception that the lipstick retains a freshlyapplied feeling on the lips over a long period of wear, meaning that thefeeling of the lipstick remains unctuous over that time. This examplequantifies the unique rheology based on viscosity measurements overrepeated shear cycles.

The conventional wax-based lipstick studied in this example has theformulation provided in Table 7.

TABLE 7 Wax-Based Lipstick Weight % Component Function 5.00 Micro WaxWhite Wax 3.00 Polyethylene-Linear Pl Wax 5.50 Ozokerite 170-D Wax 2.50Stearyl Dimethicone Wax 10.50 Diglyceryl Diisostearate Esters 8.00Glyceryl Triacetyl Hydroxystearate Esters 3.00 PolyglycerolDiisostearate Esters 7.50 Myristyl Lactate Esters 4.50 C10-30Cholesterol Esters 10.00 Squalane Oil 20.46 Caster Oil Oil 3.20Polybutene Film former 0.12 Acrylate Copolymer E0603 Film former 2.50PPG-51/SMDI Copolymer 1.00 Nylon Powder Slip Aid 0.50 Silica HighAbsorbing Particulate based gelling agent 0.50 Caprylyl GlycolPreservative 10.85 Colorants Colorants 1.25 Pearls And Mica ReflectivePearls 0.12 Fragrance Fragrance

The ETPEA gel-based lipstick according to the invention employed in thisexample has the formulation provided in Table 8.

TABLE 8 ETPEA Gel-Based Lipstick Weight % Component Function 8.00Polyethylene-Linear Pl high melting wax 95° C. 4.00 Carnauba Wax LowMelting wax 18.00 SYLVACLEAR ® C75V ETPEA gellant 0.10Polyphenylsilsesquioxane Silicone T-resin gellant 5.00 JojobaOil/Gellants/Bht Hydrocarbon gellant 1.75 Isopropyl Isostearate Ester4.70 Diisostearyl Fumarate Ester 10.00 Isohexadecane Hydrocarbon BasedOil 9.95 Hydrogenated Polyisobutene Hydrocarbon Based Oil 2.62 CastorOil Preserved Hydrocarbon Based Oil 3.14 Octyldodecanol HydrocarbonBased Oil 0.60 PERFLUOROPOLY (ME) Silicon Based Oil (ISOPR) ETH HC041.00 Perfluorononyl Dimethicone - Silicon Based Oil Hi Mw 3.14 DiphenylDimethicone Silicon Based Oil 5.00 Sucrose Acetate Isobutyrate FilmFormer 1.00 Acrylates Copolymer/Isododecane Film Former 0.50 GlycerylRosinate-Food Grade Film Former 5.24 Lanolin Acetate Film Former 7.00Ethylhexyl-Methoxycinnamate Sunscreen 2.00 Octocrylene Sunscreen 0.50Caprylyl Glycol Preservative 0.01 Sucralose Sweetener 5.83 Pigments &Pearls Colorants 0.15 Fragrance Fragrance

FIG. 4 shows the viscosity of a conventional wax-based lipstick over afirst shear cycle (⋄) and a second shear cycle (□). As can be seen, theviscosity of the composition is a function of shear rate, such that theviscosity of the composition decreases during the first shear cycle ofthe entire range of shear rates. Notably, during the second shear cycle,the composition does not retain the initial viscosity achieved at theonset of the first shear cycle. Rather, the viscosity is seen to fall toless than 10 Pa·sec at the beginning of the second shear cycle to lessthan 1 Pa·sec at the end of the second shear cycle. The viscosity lossseen throughout the second shear cycle is the results of the degradationof the wax structure during the first shear cycle.

FIG. 5 shows the viscosity of a lipstick according to the invention overa first shear cycle (⋄) and a second shear cycle (□). The viscosity overthe first and second shear cycles remain nearly identical over theentire range of shear rates. While some deviation is seen during thesecond shear cycle at very high shear rates, the deviation is minimalover the range of shear rates from 1 to 10 sec⁻¹ which corresponds toshear rates typically encountered during wear. This resistance to shearinduced degradation is believed to result from the elastic nature of thegel such that hydrogen bonds are broken to accommodate shear andreformed to restore the gel-network when the shear is released.

The lipstick of the invention shown in FIG. 5 was found to have an oily,moisturizing feeling when initially applied and to retain that feelingthrough repeated cycles of rubbing the lips together over time.

All patents and patent publications referred to herein are herebyincorporated by reference.

Certain modifications and improvements will occur to those skilled inthe art upon a reading of the foregoing description. It should beunderstood that all such modifications and improvements have beendeleted herein for the sake of conciseness and readability but areproperly within the scope of the following claims.

1.-129. (canceled)
 130. A method for imparting an unctuous film to thelips comprising applying thereto a composition comprising: (a) from 0.1to 2.5% by weight of a copolymer or copolymers having an averagemolecular weight between 3,000 and 7,500 Daltons and being capable offorming a gel with low-polarity and nonpolar oils at or below a sol-geltransition temperature T_(gel) wherein T_(gel) is above bodytemperature; (b) from 5 to 12% by weight of a first wax component havinga melting point above T_(gel); wherein said first wax component equalsor exceeds, on a weight basis, the amount of said copolymer orcopolymers; (c) from 5 to 12% by weight of a second wax component havinga melting point at or below T_(gel); and (d) from 40 to 80% by weight ofone or more low-polarity or nonpolar ester oils capable of forming a gelwith said copolymer or copolymers at or below said sol-gel transitiontemperature T_(gel); wherein the weight ratio of the copolymer orcopolymers copolymer to the ester oils is less than 1:30; and whereinsaid ester oils comprise an oil selected from triisostearoylpolyglyceryl-3 dimer dilinoleate, diisopropyl dimerate, triisostearyltrilinoleate, C₁₂₋₁₅ alcohols benzoate, octyldodecyl stearoyl stearate,diisostearyl fumarate, polyglyceryl-2 diisostearate/IPDI copolymer, andcombinations thereof; wherein said composition is self-supporting atroom temperature and is further characterized by a viscosity measuredduring a second shear cycle that is within ±20% of the viscositymeasured during a first shear cycle at every shear rate between 1 and 10sec⁻¹, wherein said first and said second shear cycles are identical andcomprise increasing shear rates from 1 to 1,000 sec⁻¹.
 131. The methodof claim 1, wherein the copolymer or copolymers having an averagemolecular weight between 3,000 and 7,500 Daltons and being capable offorming a gel with low-polarity and nonpolar oils at or below a sol-geltransition temperature T_(gel) wherein T_(gel) is above body temperatureis comprised of Bis-Stearyl Ethylenediamine/Neopentyl Glycol/StearylHydrogenated Dimer Dilinoleate.
 132. The method of claim 131, whereinthe first wax component comprises silicone waxes having a melting pointbetween about 53 and 75 C.
 133. The method of claim 131, wherein thesecond wax component comprises cocoa butter.
 134. The method of claim131, wherein the first wax component comprises silicone waxes having amelting point between about 53 and 75 C and the second wax componentcomprises cocoa butter.
 135. The method of claim 131 wherein theviscosity measured in said second shear cycle is within ±10% of theviscosity measured during said first shear cycle at every shear ratebetween 1 and 10 sec⁻¹.
 136. The method of claim 131 wherein theviscosity measured in said second shear cycle is within ±5% of theviscosity measured during said first shear cycle at every shear ratebetween 1 and 10 sec⁻¹.
 137. The method of claim 131 furthercharacterized by a viscosity measured during said second shear cyclethat is within ±20% of the viscosity measured during said first shearcycle at every shear rate between 10 and 100 sec⁻¹.
 138. The method ofclaim 131 further characterized by a viscosity greater than 50 Pa·sec ata shear rate of 1 sec⁻¹ as measured during said first shear cycle. 139.The method of claim 131 further comprising a silicone T-resin.
 140. Themethod of claim 139 wherein said silicone T-resin comprises siloxymoieties of the form:[RSiO_(3/2)]_(a)[R¹SiO_(3/2)]_(b)[R²SiO_(3/2)]_(c)[R³ ₃SiO_(1/2)]_(d)[R³₂SiO_(2/2)]_(e)[SiO_(4/2)]_(f) where R is methyl; R¹ is C₂₋₂₀ alkyl orC₅₋₂₀ cycloalkyl; R² is phenyl, R³ is C₁₋₂₀ alkyl, C₅₋₂₀ cycloalkyl,C₇₋₁₄ aralkyl, C₇₋₁₄ alkaryl, or C₆₋₁₀ aryl; and a, b, and c are suchthat their respective siloxy groups together comprise at least 90 molpercent of the total of siloxy moieties, and d, e, and f are such thattheir respective moieties together comprise less than 10 mol percent ofall of siloxy moieties.
 141. The method of claim 140 wherein saidsilicone T-resin is a polyphenylsilsesquioxane.
 142. The method of claim140 wherein said silicone T-resin has a refractive index of at least1.5, measured as a film at 25° C.
 143. The method of claim 140 whereinthe average molecular weight of said silicone T-resin is between 5,000and 6,000 Daltons.
 144. A method for imparting an unctuous film to thelips comprising applying thereto a composition comprising: (a) from 0.1to 2.5% by weight of a copolymer or copolymers having an averagemolecular weight between 3,000 and 7,500 Daltons and being capable offorming a gel with low-polarity and nonpolar oils at or below a sol-geltransition temperature T_(gel) of 70° C. to 85° C.; (b) from 5 to 12% byweight of a first wax component having a melting point above T_(gel);wherein said first wax component equals or exceeds, on a weight basis,the amount of Bis-Stearyl Ethylenediamine/Neopentyl Glycol/StearylHydrogenated Dimer Dilinoleate copolymer; (c) from 5 to 12% by weight ofa second wax component having a melting point at or below T_(gel); and(d) from 40 to 80% by weight of one or more low-polarity or nonpolarester oils capable of forming a gel with said ester terminatedpoly(ester-amide) polymer at or below said sol-gel transitiontemperature T_(gel); wherein the weight ratio of Bis-StearylEthylenediamine/Neopentyl Glycol/Stearyl Hydrogenated Dimer Dilinoleatecopolymer to said ester oils is less than 1:30; wherein said ester oilscomprise an oil selected from triisostearoyl polyglyceryl-3 dimerdilinoleate, diisopropyl dimerate, triisostearyl trilinoleate, C₁₂₋₁₅alcohols benzoate, octyldodecyl stearoyl stearate, diisostearylfumarate, polyglyceryl-2 diisostearate/IPDI copolymer, and combinationsthereof; wherein said composition is self-supporting at room temperatureand is further characterized by a viscosity measured during a secondshear cycle that is within ±20% of the viscosity measured during a firstshear cycle at every shear rate between 1 and 10 sec⁻¹, wherein saidfirst and said second shear cycles are identical and comprise increasingshear rates from 1 to 1,000 sec⁻¹; and wherein said composition ischaracterized by: (i) a viscosity greater than 100 Pa·sec at shear ratesbetween 1 and 5 sec⁻¹ when measured during said first and second shearcycles; and (ii) a viscosity greater than 10 Pa·sec at shear ratesbetween 10 and 50 sec⁻¹ when measured during said first and second shearcycles; and (iii) a viscosity greater than 1 Pa·sec at a shear rate of100 sec⁻¹ when measured during said first and second shear cycles. 145.The method of claim 144 further comprising from about 0.1 to about 8% byweight of a silicone T-resin.
 146. The method of claim 144 wherein saidsilicone T-resin is a polyphenylsilsesquioxane.
 147. The method of claim144 wherein the silicone T-resin is a polyphenylsilsesquioxane.
 148. Themethod of claim 144, wherein the first wax component comprises siliconewaxes having a melting point between about 53 and 75 C.
 149. The methodof claim 144, wherein the second wax component comprises cocoa butter.